Emulsifier is an organic compound that encompasses in the same molecule two dissimilar structural groups e.g. water soluble and a water insoluble moiety. It is the ingredient which binds the water and oil in a cream or lotion together permanently. The composition, solubility properties, location and relative sizes of these dissimilar groups in relation to the overall molecular configuration determine the surface activity of a compound. Emulsifiers are classified on the basis of their hydrophilic or solubilizing groups in to four categories anionic, non ionic, cationics and amphoterics. Emulsifier is utilized in various industries; agriculture, building and construction, elastomers & plastics, food & beverages, industrial cleaning, leather, metals, paper, textiles paints & protective coatings etc. An emulsion is an ideal formulation for the administration. The emulsion form allows uniform application of a small amount of active ingredient on the surface of the skin. Some of the important emulsions in different field are pharmaceutical emulsions, rosin & rubber emulsion, textile emulsions, pesticide emulsions, food emulsions, emulsion in paint industry, emulsion in polish industry, leather & paper treatment emulsions etc. Various cosmetics creams, such as moisturizers, contain emulsifiers. Lighter, less greasy feeling creams are oil in water emulsions; heavier creams used to treat rough skin are water in oil emulsions, with oil as the main ingredient. Liquid soaps, toothpastes and other body care products also contain emulsifiers. Emulsifiers have the ability to optimize the concentration of certain nutrients in an emulsion. For example, in hair conditioners, some conditioning agents can damage hair if not properly diluted in the solution. Emulsifiers are among the most frequently used types of food additives. Emulsifiers can help to make a food appealing. Emulsifiers have a big effect on the structure and texture of many foods. Increasing demand for low fat food among health conscious consumers is gradually driving the market for emulsifiers. Besides stabilizing emulsions, emulsifiers derived from non hydrogenated fats help in maintaining sensory characteristics of food such as texture, flavor, and taste that are often lost due to fat reduction. This characteristic of making healthier products similar in taste to fat containing versions has enabled emulsifiers in gaining widespread acceptance in the market. The global food industry is also witnessing increase in demand for multipurpose emulsifiers that perform functions of both stabilization and emulsification.
Some of the fundamentals of the book are characteristics and application of emulsifiers, wetting and detergent structures in emulsifier, effect of surfactant on the properties of solutions, wetting characteristics of emulsifiers, formulated emulsifiers, non surfactant functional additives, inert fillers, functional surfactant additives, uses of emulsifiers, household and personal products, industrial uses of emulsifier, anionic surfactants, non ionic surfactants, cationic, amphoteric and enzyme, alkylolamides, vinylarene polymers, alkyl sulfates, ethoxylation processes, application of emulsifiers, etc.
The present book contains manufacturing processes of various types of emulsifiers which have applications in different industries. This is a resourceful book for scientists, technologists, entrepreneurs and ingredients suppliers.
1. Characteristics and Application of
Introduction, Classification of Emulsifiers,
Solubility & Surface Activity of Emulsifi-
ers, Wetting and Detergent Strucures in
Emulsifier, Effect of Surfacant on the Pro- perties of Solutions, Wetting Charcteristics of Emulsifiers, Micellar Sol- uilization of Emulsifiers, Formulated Emulsifiers, Non- Surfactant Functional Additives, Inert Fill- ers, Functional Surfactant Additives, Uses of Emulsifiers, Household and Personal Products, Industrial Uses.
2. Industrial Uses of Emulsifier
Agriculture, Building and Construction, Elastomers and Plastics, Food and Beve- ra ges, Industrial Cleaning, Leather, Metals, Paper, Paints and Protective Coatings, Pe- troleum Production and Products, Textiles, Biodegradable Emulsifiers and Water Poll- ution, Biodegradation, Water Pollution, Re- cent Trends.
3. Anionic Surfactants
Introduction,Carboxylates, Soap, N-Acyls- arcosinates, Acylated Protein Hydrolysates, Sulfonates, Alkyl benzene Sulfonates, Pet- roleum Sulfonates, Dialkyl Sulfosuccinates, Naphthalene Sulfonates, N-acyl-N-alkyl- taurates, 2-Sulfoethyl Es-ters of Fatty Acids, Olefin Sulphonates, Sulfates & Sulfated fates (Sulfated Alcohols), Sulfated Natural Fats and Oils,Sulfated Alkanolamides, Sulfated Esters, Ethoxylated and Sulfated Alkyl
phenols, Ethoxylated and Sulfated Alco- hols, Phosphate Esters.
4. Non-Ionic Surfactants
Introduction, Polyoxyethylene Surfactants,
Ethoxylated Alkyl Phenols, Eth -oxylated
Aliphatic Alcohols, Carboxylic Esters, Gl-
ycerol Esters, Polyethylene Glycol Esters,
Anhydrosorbitol Esters, Ethoxylated Anh-
ydrosorbitol Esters, Glycol Esters of Fatty
Acids, Ethoxylated Natural Fats, Oils and
Waxes, Carboxylic Amides, Diethanolami- ne Condensates, Monoalkanolamine Co- ndensates, Poly- oxyethylene Fatty Acids Amides, Poly- alkylene Oxide Block Cop- olymers, Poly- oxypropylene-Polyoxyeth- ylene Derivatives, Organo Silicones Deri- vatives.
5. Cationic, Amphoteric and Enzyme
Cationic Detergents, Amines not containing Oxygen, Oxygenâ€” Containing Amines,
Except Amides, Amine Oxides, Polyoxy e-
thylene Alkyl and Alicyclic Amines, 2-Alkyl- 1-(hydroxy- ethyl)-2-imidazolines, N, N, Nâ€™ Nâ€™
-Tetrakis-substituted Ethylen ediamines, Other
Miscellaneous Cationic Surfactants, Amines Having Amide Linkages, Quaternary Ammon- ium Salts, Amphoteric Surfactants, Enzyme Detergents.
6. Sulfonated Oils
Historical Background, Chemistry of Sulfation
and Sulfonation, Applications of Sulfonated Oils,
Manufacture of Sulfonated Oils, Sulfation, Sulfonation, Sulfation of individual Oils, Characteristics and Analysis of Sulfonated Sulfated Oils.
Introduction, Alkylolamides in Shampoo Formulations, Chemistery of the Alkylola- mides, Mono-Alkylolamides, Di-Alkylola- mides, Pure Di-Alkyl olamides, Phosphox- ylated Alkylolamides, Sulphated Alkylola- mides, Foam Stabilization, Manufacture of Alkylol- amides, Coconut Fatty Acid Die thanolamide, Lauric Acid Dieth anolamide, Oleic Acid Monoethan olamide, Stearic Acid Mono ethanolamide.
8. Vinylarene Polymers
Monomers, Anionic Polymerization, Polymer
Reactions, Stereoregular Polymerization, Ca- tionic Polymerization, Free-Radical Polymeri- zation, Polymer Properties, Electrical Proper- ties, Utility and Application.
Introduction, Applications of Igepon T Produ- cts, Future of Igepons, Manufacture of Igepon T, Raw Materials, Oleic Acid Chloride, Igepon T Gel, Igepon T Powder, Chemical Control,Ut- ilities, Materials of Construction.
10. Vinylamine Polymers
Preparation, Polymerization Followed by Hy- drolysis, Polymerization Followed by Reduc- tion, Hofmann Degradation of Poly(acrylamide), Polymerization Kinetics, Copolymers of Vinyl-,
Amine Properties, Chemical Reactions of Poly
11. Alkyl Sulfates
Introduction, Manufacture of Alcohols, Pro- perties and Performance Characteristics of Alkyl Sulfates, Krafft Point, Critical Micelle Concentration, Surface and Interfacial Tens- ions, Wetting Time, Foam Height, Detergen- cy, Dishwashing Test, Emulsion Stability, M- anufacture of Alkyl Sulfates, Sulfation with Chlorosulfonic Acid, Sulfation with Sulfuric Acid, Sulfation with Sulfur Trioxide, Manuf- acture of Alkyl Sulfated on Large Scale, For- mulated Products from Alkyl Sulfates.
12. N-Vinyl Amide Polymers
Monomers, Manufacture, Polymerization, Pr- operties of Poly( vinyl Amides), Other Poly(vi- nyl Amides), Uses, Cosmetics and Toiletries, Textiles and Dyes, Pharmaceuticals, Adhesi- ves, Beverage Clarification, Miscellaneous Uses,
Specifications and Standards, Analytical and Test Methods, Health and Safety Factors.
13. Olefin Sulfate and Sulfonates
Introduction, Olefin Sulfates, Raw Materials and Product Composition, Olefin Sulfates from Shale Oil, Olefin Sulfate from Wax Cracked Distillates, Sulfation, Neutralization and Hydrolysis, Evaporation, Finishing, Solvent Recovery, Olefin Sulfates, Introduction, Products of Sulfonation, Manufacture of Olefin Sulfonates Introduction, Batch Sulfonation, Continuous
Sulfonation, Sulfonation with Dioxane- SO3 , Characteristics & Surface Active Properties of Olefin Sulfonates, Formulat- ed of Heavy-Duty Detergents with Ole- fin Sulfonates.
14. Ethoxylation Processes
Introduction, Ethoxylated Alkyl Phenols, Laboratory Method of Preparation, Batch Ethoxylation Unit, Properties of Ethoxyl- ated Alkyl Phenols.
15. Ethoxylated Fatty Alcohols
Introduction, Laboratory Method of Prep- aration, Continuous Ethoxylation Unit, Pro- perties of Ethoxylated Fatty Alcohols, Sol- ubility, Cloud Point, Surface and Interfacial Tension, Detergency, Wetting Properties, Foaming Properties, Emulsifying Properties, Ethoxylated Fatty Acids, Introduction, Manu- facture, Properties of Fatty Acid Ethoxylates, Ethoxylated Fatty Amines, Formulations.
16. Alkyl Phenol Ether Sulfates
Introduction, Sulfation and Sulfonation, Man- ufacture of Alkyl Phenol Ether Sulfates, Sul- famation, Nonylphenol 4-ethoxy Sulfate, Di- (isohexyl / isoheptyl)phenol Ether Sulfate, Do- decylphenol Ether Sulfate, Sulfation with Sulfur Trioxide, Comparison of Sulfation with Sulfur Trioxide and Sulfamic Acid, Properties and Performance Characteristics of Alkyl Phenol Ether Sulfates.
17. Alkyl Ether Sulfates
Introduction, Properties & Performance Char- acteristics of Alkyl Ether Sulfates, Individual
Alkyl Ether Sulfates, Tallow Alcohol Ether Su- lfates, Manufacture of Alkyl Ether Sulfates, Process Development, Manufacture of Alcohol Ether Sulfates, Formulated Products From Alkyl Ether Sulfates.
18. Fatty Amine Oxides
Introduction, Manufacture of Fatty Amine Oxi- des, Routes to Fatty Amines, Amine Oxidation, Commercial Synthesis, Properties and Analysis of Fatty Amine Oxides, Amine Oxide Propert- ies, Analytical Methods, Formulations and Use of Fatty Amine Oxides, Light- Duty Liquids, He- avy Duty Formulations.
19. Bisquaternery and Other Cationic
Introduction, Preparation of Bisqu- aterneries, 2- Butene-Bridged-Bisquat erneries,Dip-henyloxide- Bridged-Bis- quaterneries, Die- thyleneoxide-Bri- dged- Bisquaterneries, p-Xylylene-Bridged-Bisq- uaterneries,2-Butyne-Bridged-Bis- quaterneries, Performance Evaluation of Softeners, Multiwash Softeners Evaluati- on, Softness Evaluation, Rew- ettability Measurements, Performance Characteri- stics of Bisquaterneries and Other Cationics Soft- eners, Softener Concentration, Fabric Rew- ettab- ility Measurements.
20. Other Miscellaneous Emulsifiers
(i) Alkyl Naphthalene Sulfonates
Introduction, General Method of Manufacture, Nekal â€˜BXGâ€™, Nekal â€˜BXâ€™ Extra Strong, Dibutyl Naphthalene Sulfonate, Diamyl Naphthalene Sulfonate.
(ii) Sulfated Alkylolamides
Introduction, Igepon â€˜Bâ€™ Paste, Igepon â€˜Câ€™ Paste, Sodium-N-2-hydroxyethyl-hexa decanamide H Sulfate.
(iii) Sodium B-Sulfoethyl Esters of Fatty Acids
IntroductionÂ¬, Manufacture of Igepon A.
(iv) Polyethylene Glycol Fatty Acid Esters
Introduction, Manufacturing Process, Fatty Acid Esters of Sucrose.
Introduction, Manufacture of Sodium N- Oleoylsarcosinate.
(vi) Sulfated Monoglyceride
21. Application of Emulsifiers
(i) Pharmaceutical Emulsions
Introduction, Cod Liver Oil Emulsions, Oint- ments, Beelerâ€™s Base, Washable Ointment Base, Greaseless Base, Ointment Washable Type, Steroidal Emulsion, Aeriflavine Oint- ment, Aluminium Acetate Lotion, Typical Antibiotic, Anesthetic and Anti-Inflammatory Ointment, O/W Type Benzyl Ointment, O/W Boric Acid Ointment, W/O Calamine Cream, W/O Emollient Ointment, Solubilized Hexach- lorophene, O/W Oxyquinoline Sulphate Oint- ment, Penicillin Ointment.
(ii) Rosin and Rubber Emulsion
Rosin Emulsion, PVA Resin Emulsion, Pent- aerythritol Abietate Emulsion, Methyl Meth- acrylate Emulsion, Polystyrene Resin Emulsion,
Polyvinyl Ether Emulsion, Synthetic Rubber Emulsion Polymerization, Chlorinated Rubber Emulsion, Wall Tile Adhesive, Black Industrial Cement, Reclaim Asphalt Dispersion Cement, General Purpose Cement, Rubber Dressing.
Antistatic Textile Dressing, Lustre Emulsion for Starching, Rootproofing Emulsion, Textile Soft- eners, Textile Gloss Oil, Yarn Finish, Soluble Textile Oil, Rope Preservative, Synthetic Thread Lubricant, Acetate Rayon Oil, Screen Printing Emulsion, Mineral Oil Emulsion, Rayon Delustering.
(iv) Pesticides Emulsions
Malathion Wettable Powder, Dieldrin Formulation, Lindane Formulation, Ronnel Formulation, Butyl Ester of 2, 4-D Formulation, Fruit Coating Wax Emulsion, Cattle Dips, DDT Formulation, Chlor- dane Formulation, Heptachlor Formulation, Aldrin Formulation, Endrin Emulsion Concentrate.
(v) Food Emulsion
Chocolate Milk, Stabilized, Artificial Cream, Le- mon Oil Emulsion, Transparent Lemon Oil Emul- sion, Orange Emulsion, Bitter Almond Emulsion, Butter Substitute, Mayonnaise, Salad Dressings, Coffee Whitner Liquid, Coffee Whitner (Spray Dried), Ice Cream Mix, Pickle Flavour Emulsion, Starch Paste.
(vi) Emulsions in Paint Industry
Flat Interior Paint, Semigloss White Latex Paint, Gloss Emulsion Paint, Exterior Latex Paint, Exterior White Paint, Interior White Paint, Resin Oil Emulsion.
(vii)Emulsions in Polish Industry
Automobile Polish, â€˜Dry Brightâ€™ Floor Polish, Paste Polishes, Mineral Oil Emulsion Polishes, Silicone Polishing Cloth, Paste Type, Automobile Cleaner Polish.
(viii)Leather and Paper Treatment Emulsions
Leather Finishes, Fat Liquors, Leather Dressing,
Shoemakerâ€™s Wax Burnishing Polish, Softner for Leather Goods, Leather Pasting, Coating for Paper, Water Resistant Coating for Paper, Grease Resistant Paper Coating.
(ix) Cutting Oils, Soluble Oils, Miscible Oils
Napthenic Miscible Oils, Cutting Oils, Mold Release Compound.
All Purpose Cleaners, Pine Base Cleaner,
Hand Dishwashing Detergent, Machine Dish- washing Liquid, Household Heavy Duty Dete- rgent, Household Light Duty Detergent, Fine Fabric Detergent, Hydrogen Peroxide Emulsions, Floor Wax Remover, Rug Cleaner, Shoe Cleaner, Waterless Hand Cleaners, Acid Aluminium Clea- ner, Copper Cleaner, Degreaser Formulation, Light Duty Steam Cleaner, Alkaline Cleaner, Merceriza- tion Formulation, Powdered Caustic Bottle Wash- ing Compound, White Wall Tire Cleaner.
22. Determination of Physical Surface
Active Characteristics of Emulsifiers
Introduction, Physical Characteristics, Density of Powdered Detergents, Apparent Bulk Density, Cup Density, Particle Size of Powdered Deterge- nts, Hand Sieving, Machine Sieving, pH and Alk-
alinity, Free Alkalinity, Cloud Point of Non-ionic Detergents, Viscosity, Surface-Active Properties, Ring Method, Experimental Procedure, Determina- tion of Surface Tension, Determination of Interfac- ial Tension, Calculation of Surface Tension, Calcul- ation of Interfacial Tension, Performance Characte- ristics, Dishwashing Tests, Laundry Evaluation, Split Item Tests, Bundle Test, Foam Tests, Dynamic Foam Test, Pour Foam Test, Wetting Test, Canvas Disc Test, Skein Test.
23. Analysis of Emulsifiers
Introduction, Separation of Surfactants, Identi-
fication of Components, Anionics, Cationics, Non-ionics, Determination of Surfactants, Total Organic Active Ingredient, Procedure, Correction for Sodium Chloride Content, Anionic Surfactants, Preliminary Estimate of Mol. Wt., Titration with Cationic Surfactants, Prepa raition and Standardiz- ation of Titrant, Titration of Sample, Amine Comp- lexation MethodÂ¬, Determination of Alkylaryl Sulf- onates, Determination of Alkylaryl Sulfonates in the Presence of Short Alkyl Chain Sulfonates, et- erniination of Fatty Alcohol Sulfates, Cationic Sur- factants, Determination of Amine Oxides, Non-Ionic Surfactants, Column Techniques, Batch Technique, Tooth Powders, Bath Powders, Light-Duty Liquid Detergent.
and Application of Emulsifiers
is an organic compound
that encompasses in the same molecule two dissimilar structural groups
soluble and a water insoluble moiety. The composition solubility
and relative sizes of these dissimilar groups in relation to the
molecular configuration determine the surface activity of a compound.
soluble moiety is generally referred to as hydrophilic lipophobic and
oleophobic and the water insoluble moiety is called hydrophobic
oleophilic. A surfactant in general possesses the following
It must be
soluble in at least one phase of a liquid system. Its molecules are
groups with opposing solubility tendencies. At the interphase of a
system it must form oriented monolayers and its equilibrium
concentration at a
phase interface is greater than its concentration in the bulk of the
It forms micelles if the concentration of the solute exceeds a limiting
in the bulk of the solution. Solutions of surfactants exhibit
wetting emulsifying solubilizing and dispersing properties either
Classification of Emulsifiers
classified on the basis of their hydrophilic or solubilizing groups
into four categories
anionics non ionics cationics and amphoterics. The anionic solubilizing
are carboxylates sulfonates sulfates and phosphates. Non ionics are
by hydroxyl groups and polyoxyethylene chains. Primary Secondary and
amines and quaternary ammonium groups are the cationic solubilizers.
surfactants are solubilized by some combination of anionic and cationic
moieties non ionic solubilizing groups may also be part of amphoteric
molecules. In addition to the primary solubilizing groups other
units c ntribute to the hydrophilic tendencies of molecules e.g. ester
and amide linkages. The hydrophobic i.e. lipophilic moieties are almost
invariably hydrocarbon or halogen substituted hydrocarbon groups.
linkages are less hydrophobic than carbon to carbon single bonds.
based on silicon containing hydrophobes are just beginning to be
Solubility & Surface Activity of Emulsifiers
solute usually displays maximum surface activity and functional
when it is near the threshold of insolubility. Moreover the solubility
surfactants is markedly affected by temperature and electrolyte
Thus for each set of conditions there is usually an optimum solubility
for each type of surfactant. Relatively small changes in the
composition of a
surfactant are often sufficient to change its solubility and hence its
activity. There are many ways to effect such changes for example the
molecular weight of the raw material mixture i.e. hydrophobe can be
slightly or the degree of sulfation sulfonation or ethoxylation can be
increased or decreased. Empirical solubility tests rank with charge
chemical analysis as control techniques for surfactant manufacturing
They make it possible to produce to tight specifications by
variations in successive lots of raw materials or to adjust a process
a range of optimum performance conditions for essentially the same
are pointed to different uses.
Wetting and Detergent Structures in Emulsifier
properties with molecular structures have been sought by numerous
investigators. One result has been the identification of strong wetting
strong detergent structures. The hydrophilic group of strong wetting
located at the middle of the hydrophobic chain or at the central
point if the molecule contains two or more chains. Conversely the
group in strong detergents is located at the end of the hydro
and Application of Emulsifiers phobic chain.
wetting and detersive properties of unformulated anionic and non ionic
compounds follow this structural pattern usefulness of the
limited to the selection of surfactants for a few specialized
textile wetting agents. This limitation is due to the pronounced
formulated or built products over pure compounds for detergency
etc. In formulations detergency and wetting strength of individual
lose much of their significance. Textile wetting efficiency is not
related to surface tension lowering but dilute aqueous solutions of
wetting agents characteristically have low surface tensions.
Effect of Surfactant on the Properties of Solutions
changes the properties of a solvent in which it is dissolved to a much
extent than would be expected from its concentration. This marked
effect is due
to (1) adsorption at the solution interfaces (2) orientation of the
surfactant ions of molecules (3) miscelle formation in the bulk of the
and (4) orientation of the surfactant ions or molecules in the
effects are caused by the amphipathic structure of a surfactant
the magnitude of the effects depends to a large extent on the
balance of the molecule. An efficient surfactant is usually relatively
insoluble as individual ions in the bulk of a solution.
Wetting Characteristics of Emulsifiers
solid by a surfactant solution may represent either the displacement of
some other gas from the solid surface by the solution of a liquid e.g.
an oil from
the solid surface. Wettability represents the tendency of a solid to be
and wetting power the tendency of a liquid to wet a solid. The wetting
liquid by another immiscible liquid is visually apparent by the
spreading of a
film to create a large liquid liquid interface and lack of wetting is
by the tendency of one liquid to form droplets in the form of a lens on
surface of the other.
between a solid or liquid to be wetted and the wetting solution
degree or completeness of wetting that can be attained. In practical
applications the speed of wetting may be as important as the
wetting at equillibrium.
investigators have pointed out that rate of migration of surfactant
from the bulk of the solution to maintain the concentration of the
one limiting factor on the speed of wetting. Dynamic methods for
the lowering of surface free energy have been used to estimate the
of this factor. The effectiveness of mechanical agitation thermal
capillerity in bringing the solid or liquid to be wetted quickly into
contact with the wetting solution often influences the speed of wetting
than the migration rate of the surfactant.
Micellar Solubilization of Emulsifiers
dissolutions of a normally insoluble substance by a relatively dilute
of a surfactant are called Solubilization. The substance dissolved is
to as the solubilizate and the surfactant as the solubilizer. There are
simple quantitative relationships between solubilizing power of a
and the micellar or surface properties of its solutions. Solubilization
primarily a phenomenon of importance in dilute solutions. In more
solutions it is sometimes difficult to distinguish between
cosolvency which is a term applied to a mixture of solvents that takes
solution a higher concentration of solute than would be expected from
of their individual Characteristics and Application of Emulsifiers
powers. Solubilization does not introduce another phase and solutions
containing solubilized material are thermodynamically stable. It is a
phenomenon but the rates of attainment of equilibrium differ greatly
approached from different directions.
molecules or ions at concentrations above a minimum value
each solvent solute system associate into aggregates called micelles.
critical micelle concentration (CMC) is used to denote the
which micelles start to form in a system comprising solvents
other solutes and a defined physical environment. The CMC of
aqueous solutions depends on the structure of the compounds and the
but for many anionics at low electrolyte concentrations and room
is close to 10 2 mols/litre for non ionics under comparable condition
less about 10 4 moles/litre. In many surfactants where the hydrophilic
unchanged but the size of the hydrophobic group is increased CMC values
decrease with increasing size of the hydrophobe for both ionic and
types. If the hydrophobic group is held constant CMC values decrease
decreasing ethylene oxide content of non ionic. Increasing the
concentration decreases CMC values for both anionics and non ionics.
The CMC of
anionic micelles increases as the temperature increases whereas the CMC
ionics decreases with the increase in temperature as would be expected
cloud point phenomenon.
is a micellar phenomenon that occurs only at concentrations above the
is of considerable importance in non aqueous applications of
where water is the solubilizate. Typical applications are in dry
solutions and engine lubricants. Essential oils vitamins cosmetic
textile mill processing oils are typical solubilizates in aqueous
Mixtures of surfactants are generally better solubilizers than the same
surfactants used individually. Ionic non ionic com binations are
surfactant products may be roughly divided into two major groups. One
designed to perform surfactant functions e.g. cleaning wetting foaming
and dispersing. The other group is designed to convey a non surfactant
functional ingredient to the point of use e.g. a herbicide or
toxicant a textile mill processing oil. In addition to primary
components of formulated surfactant products may be classified as (1)
surfactant functional additives (2) Inert fillers and (3) Functional
Non surfactant Functional Additives
The art of
surfactant formulation is directed to finding a combination of
will be compatible and perform satisfactorily at the least cost to the
Frequently a surfactant is the most expensive component of a
the mixture is designed so that less expensive inorganic additives
as much as possible to the functional performance of the product.
agents are used to solubilize the ingredients in concentrated liquid
formulations. The most common hydrotropes are the sodium or potassium
benzene cumene toluene or xylene sulfonates. These highly soluble
present at relatively high concentrations i.e. 5 15 wt percent increase
solubility of sulfonate and sulfate surfactants in concentrated aqueous
compositions. Solvents are also incorporated in surfactant products to
homogeneous concentrates and also as functional additives. For example
is used as a solvent to clarify liquid shampoos. Pine oil and/or
kerosene are often functional components of industrial and consumer
are viscous liquids or low melting solids that Characteristics and
of Emulsifiers are difficult to handle as 100 per cent active
sulfate clays or other inexpensive fillers are added as diluents and
to the concentrated surfactants to obtain free flowing dry powders.
portion of the sulfonating or sulfating reagent from the manufacturing
is neutralized and left in finished products as a filler.
Functional Surfactant Additives
builders and co emulsifiers are the most important functional additives
surfactant formulations. The fatty acid alkanolamides and the
are the outstanding examples of products in this category. They are
surfactants on the basis of their own properties but one of their
uses is to enhance the foaming and detergency of less expensive
materials e.g. LAS.
In these applications the performance of the mixture exceeds a
on the sum of the contributions of the components tested individually.
alkanolamides also increase the viscosity and emolliency of aqueous
The lipophilic emulsifiers are another group of functional surfactant
additives. Many of these materials are so hydrophobic that they have
utility when used alone but in mixtures with hydrophilic emulsifiers
exceedingly useful as co solvents solubilizers dispersants and
used in phosphate fertilizers to shorten manufacturing cycle and
during storage. In spray applications of herbicides insecticides and
they are used in wetting dispersing and suspending of powdered
emulsification of pesticide solutions to promote wetting spreading and
penetration of the toxicant.
Building and Construction
prevent stripping by improving the bond of asphalt to gravel and sand.
use promote air entrainment in concrete for control of density
insulating properties etc.
Elastomers and Plastics
polymerization they effect the emulsification of monomers by
monomers and catalyst which react in surfactant micelles. They also
stabilization of latexes. In foamed polymers they effect the
air and control of cell size. In latex adhesive they promote wetting
improve bond strength. In plastic articles they are used as antistatic
and in plastic coating and laminating they are used as wetting agents.
Food and Beverages
processing plants they are used for cleaning and sanitizing walls
process equipment. They give improved removal of pesticide residues and
wax coating of fruits and vegetables. In bakery products and ice cream
solubilize flavor oils control consistency and retard staling. In
solubilize flavor oils. In crystallization of sugar they improve
reduce processing time. In frying with cooking fats and oils they
spattering due to superheating and sudden volatilization of water.
cleaning janitorial supplies and clothes they are used for cleaning and
sanitizing walls floors windows vehicles engines etc. and as detergents
laundry and dry cleaning. In descaling they are used as wetting agents
corrosion inhibitors in acid cleaning of boiler tubes and heat
wax strippers they are used to improve wetting and penetrations of the
industry they are used as detergent and emulsifier in degreasing skins
promote wetting and penetration in tanning as emulsifiers in fat
hides to promote wetting penetration and leveling in dyeing.
of ores they are used for wetting and foaming i.e. collecting and
ore flotation. In cutting and forming of metals they are used for
lubrication and corrosion inhibition in rolling oils drawing lubricants
and grinding compounds. In casting they are used as mold release
rust and scale removal they are used for wetting foaming and corrosion
inhibition in pickling and electrolytic cleaning. In electroplating
used for wetting and foaming in electrolytic plating baths.
treatment they are used for derinsification pitch dispersion and
paper machine they are used fordefoaming felt washing colour leveling
dispersing. In calendaring they are used for wetting and leveling in
and colouring operations. In towels and pads they are used for wetting
improve absorption of moisture. Industrial Uses of Emulsifier
Paints and Protective Coatings
preparation they are used for flushing i.e. promote preferential
wetting by the
paint vehicle dispersing and wetting of the pigment during grinding. In
paints they are used to emulsify the oil or polymer disperse the
the latex retard sedimentation and pigment separation modifies wetting
rheological properties. In waxes and polishes they are used for
waxes stabilize emulsions and wet substrates in finishes for floor and
automobiles. Petroleum Production and Products they are used in
to emulsify oils disperse solids and modify rheological properties of
and completion fluids for oil and gas wells. In mist drilling they are
convert intrusion water to foam in air drilling. In work over of
wells they are used to emulsify and disperse sludge and sediment in
of wells modify wetting of formation at producing zone. In producing
are used to demulsify crude petroleum and inhibit corrosion of well
tanks and pipe lines. They are used for secondary recovery in flooding
operations to release crude oil from the formation surface i.e.
wetting. Their application in refined petroleum products include as
dispersant and corrosion inhibitor in fuel oils crank case oils and
preparation of fibres and filaments they are used as detergent and
in raw wool scouring dispersant in viscose rayon spin baths lubricant
antistat in spinning of hydrophobic filaments. In gray goods
are used for wetting and detergency in slashing and sizing formulations
and detergency in kier boiling and bleaching of cotton and carbonizing
of wool detergency
in scouring piece goods emulsification of processing oils. In dyeing
printing they are used for wetting penetration solubilization
leveling detergency and dispersion. In finishing of textiles they are
wetting and emulsification in finishing formulations softening
antistatic additives to finishes.
Biodegradable Emulsifiers and Water Pollution
household laundry detergents have been in use in largest amounts all
world as the major products of the surfactant industry for the last
years. The key ingredient that made this growth possible was ABS an
alkylbenzene sulfonate in which the alkyl group was a highly branched
tetramer. Its continued discharge in rivers and lakes results in
excessive foams in rivers and lakes causing pollution of water. This
became apparent for the first time in United States in 1950. Researches
out later soon revealed that some types of synthetic detergents were
resistant than soap to degradation in sewage treatment plants and
made in 1963 in U.S. to replace ABS the largest volume synthetic
LAS (Linear Alkylbenzene Sulphonate) a more biodegradable surfactant in
to facilitate the degradation of detergent products in sewage plants.
established that degradation of surfactants by the bacteria in sewage
plants is slower and less complete if the hydrophobic chain is branched
than linear. In the early 1950 s no economically feasible technology
for replacing ABS by a biodegradable substitute. The logical approach
problem was replacement of the propylene tetramer by an equally
linear 12 carbon alkylation feedstock from a petrochemical source.
breakthroughs in the early 1960 s opened up several possible routes to
biodegradable alkylbenzene sulfonates.
Separation of n paraffins
from kerosene feedstocks in molecular sieves (or alternatively by
with urea). Alkylation with the n paraffins involves only conventional
processing i.e. monochlorination followed by a Friedel Crafts reaction
dehydro Industrial Uses of Emulsifier halogenation and alkylation.
Synthesis of linear 1 olefin
or alcoholic detergent hydrophobes from ethylene is carried out by the
process using an aluminium catalyst. The trialkyl aluminium
this process can be oxidized to yield linear secondary alcohol suitable
detergent bases or catalytically decomposed to yield 1 olefins that can
as alkylate feedstocks or hydrated to alcoholic hydrophobes.
The 1 olefins obtained by
cracking of petroleum waxes can also be used either as alkylation
hydrated to alcoholic detergent bases.
have an inherent ability to convert organic matter including
new cell material food and energy. The predominant mechanisms by which
surfactant hydrophobes are attacked have been described as b oxidation
oxidation and aromatic oxidation. In b oxidation the most important
linear hydrocarbon chain is oxidized at two carbons at a time a branch
chain interrupts the degradation. Methyl oxidation which is less well
understood attacks terminal methyl groups. Aromatic oxidation proceeds
cat echol (1 2 benzenediol) as an intermediate which is cleaved to form
aliphatic dicarboxylic acid. The poly oxyethylene chains of non ionics
probably degraded stepwise through a carboxylation and hydrolysis
splits glycol units from the chain. From a practical viewpoint
tertiary carbons in aliphatic chains and some phenolic nuclei slow the
biodegradation process to rates that are unacceptable in present day
treatment systems. Very large polyoxyethylene chains are also degraded
In terms of products carboxylic acids and salts linear alcohol
fatty acids sulfated fatty amides sulfated esters glycol esters
and fatty alkanolamides are most readily biodegradable. The ethoxylated
sulfated linear alcohols linear alkylbenzene sulphonates and
alcohols (upto about 70 wt per cent of polyoxyethylene) are readily
biodegradable. The residual polyoxyethylene chains from high polyethene
non ionics are not surface active and are not a problem in sewage
this time. Ethoxylated linear alkylphenols are more slowly
aliphatic based non ionics. There is still some question about the
acceptability of these products for all uses. Unacceptable products on
basis of biodegradability are the branched chain substituted
derivatives branched chain substituted alkylbenzene sulfonates and the
derivatives of branched chain aliphatic alcohols i.e. sulfates or
methods to measure biodegradability of surfactants paralleled the
of biodegradable materials. Three methods out of the many screened have
received widespread acceptance. Two of these the river die away method
shake flask methods. Biodegradation Test Methods are suitable for quick
screening and/or routine use. The third a semi continuous activated
method is more time consuming but is accurate and reproducible enough
as a reference method The determination of biological oxygen demand
provides useful data on biodegradation processes.
moiety in anionic surfactants is a polar group that is negatively
aqueous solutions or dispersions. In commercial products it is either a
carboxylate sulphonate sulfate or phosphate group. In dilute alkaline
in soft water the solubilizing power of the sodium salts of the four
radicals is approximately equal and strong enough to balance the
tendency of a 12 carbon saturated hydrocarbon group the sulfate is
somewhat stronger solubilizer than the sulphonate. In neutral or acidic
or in the presence of heavy metal ions the solubilizing power of the
is markedly less than that of the other groups.
environment associated with anionic surfactants influences the
their solutions. Sodium and potassium salts are generally more soluble
and less soluble in hydrocarbons. Conversely the calcium barium and
salts are more compatible with hydrocarbon solvents and less so with
Ammonium and amine salts e.g. triethanolamine improve the compatibility
anionics with water and hydrocarbons and are widely used in
detergent applications. Higher total ionic strengths are usually
with lower solubilities of anionic surfactants. To offset this effect
molecular weight of the hydrophobe is lower in products designed for
high electrolyte concentrations. Micellar solubilization by anionics is
markedly affected by total ionic strength and also by the identity of
associated cations. The anionic surfactants can be divided into four
according to their anionic groups (1) Carboxylates (2) Sulfonates (3)
and Sulfated Products (4) Phosphate Esters.
Soaps and a
small volume of aminocarboxylates are the only Anionic Surfactants
products in the carboxylate class of surfactants. Two types of
surfactants N acy lsarcosinates and acylated protein hydrolysates are
in small quantities as specialties.
products are fatty acyl derivatives of aminocraboxylates. As compared
corresponding soaps the hydrophilic tendency of the amide linkages in
molecules is strong enough to significantly lessen inactivation of the
carboxylate ions by the calcium and magnesium ions that are present in
soap was the only surfactant produced commercially. Inspite of the
of many new surfactant types it may be noted that soap possesses some
properties which are not found in many other surfactants. The sodium
potassium cocofatty acid soaps are unexcelled as lathering and
in bar detergents for personal use in soft to medium hard water. The
C14 to C18
fatty acid sodium soaps are effective laundry and industrial detergents
to medium hard hot water. Soaps especially amine salts are excellent
emulsifiers dispersants and solubilizing agents with a wide range of
uses. Soaps have an emollient action in contact with the skin and leave
feel on textile fabrics.
lauroylsarcosinate and the sodium N acylsarcosinate derived from
acids are soap like detergents with good lathering properties. They are
principally used in dentifrices where it is claimed they also
enzymes that convert glucose to lactic acid in the mouth. N Oleoy1
is used as a textile auxiliary and detergent. The N acylsarcosinates
prepared by the condensation of a fatty acid chloride with sarcosine
methylglycine obtained from the reaction of methylamine formal dehyde
sodium cyanide) in alkaline aqueous solution.
Acylated Protein Hydrolysates
aminocarboxylates are prepared from protein hydrolysates by acylation
fatty acid chlorides or by direct condensation with fatty acids. The
products are mixtures that vary in composition from acyl derivatives of
polypeptides from incompletely hydrolyzed protein to mixtures of
acids derived from completely hydrolyzed protein. Collagen from leather
and low grade hide glues is used as a source of protein. Derivatives of
incompletely hydrolyzed peptides have a great tolerance for hard water
their effective ness as surfactants is lower.
effective structure for an anionic surfactant is a sulfonate of the
formula RSO3Na where R is a biodegradable
hydrocarbon group in the
surfactant molecular weight range. The R group can be alkyl or
the product can be a random mixture of isomers as long as it does not
chain branching that interferes with biodegradability. The surface
activity of the
oversensitive to variations in the pH or to heavy metal ions and the C
linkage is not susceptible to hydrolysis or oxidation under normal
processes on surfactant raw materials can usually be adjusted to
decrease slightly the degree of substitution of the solubilizing group
hydrophobe. The average molecular weight of the hydrophobic bases can
increased or decreased slightly. Minor adjustments in these two
produce significant differences in performance. Sulfonates are usually
in the production process as free acids that can be neutralized to form
metal salts alkaline earth metal salts or amine salts thus
another parameter for modification of properties. Manipulation of these
variables leads to products with a multiplicity of combinations of
from the same raw materials and production equipment.
of commercial importance in this group are alkylbenzene sulfonates
sulfonates di alkyl sulfosuccinates naphthalene sulfonates N acyl N
alkyltaurates 2 sulfo ethyl esters of fatty acids and olefin sulfonates.
dodecylbenzene sulfonates rank next to soaps in total usage. The sodium
linear dodecylbenzene sulfonate is commonly referred to as LAS . Linear
dodecylbenzene sulfonic acid is called LAS acid and salts other than
named in an analogous manner e.g. LAS salt. Commercial dodecylbenzene
acid is a light coloured viscous liquid that is used almost entirely as
intermediate for the manufacture of alkalimetal alkaline earth metal
of the performance of alkylbenzene sulfonates to that of aliphatic
effect of the benzene ring is often considered as approximately
three carbon atoms in an aliphatic chain.
sulfonic acids are strong organic acids and form essentially neutral
alkalimetal salts that have a good solubility in aqueous solutions at
concentrations over the entire pH range.
not sensitive to precipitation by the natural hardness of the surface
the alkaline earth metal salts are less water soluble than the alkali
amine salts. The calcium salts are sufficiently soluble in hydrocarbons
in these media. The alkylbenzene sulfonates are one of the most
stable types of surfactants. The sulfonic group is not susceptible to
ammonium alkaline hydrolysis under normal conditions of storage or use.
compounds are stable to strong oxidising agents is aqueous solutions at
concentrations and are stable in carefully formulated products
activity of unformulated unbuilt dodecyl benzene sulfonates is
strong for the salts to be useful for their detersive wetting
and foaming properties but they are not outstanding surfactants. The
usage of LAS stems from other factors which include their low cost
quality adequate supply light colour low odour and excellent response
formulation and builders. For example LAS solutions are only average
but mixtures of LAS with alkanolamine or alkylamine oxide foam boasters
excellent foaming properties. Similarly LAS performs well in built
cleaning products where the wetting foaming emulsifying and dispersing
properties of the surfactant component are as important as the
power. Amine salts of LAS & ABS acids are used in blends with
emulsifiers particularly the non ionic types in emulsifiable
sulfonates are the only large volume class of surfactants that are used
predominantly in non aqueous systems. They are available as co products
refining of certain petroleum fractions. They are usually grouped into
broad classes water soluble types called green soaps and oil soluble
called mahogany soaps (which may also be soluble in water).
are of little use. The mahogany soaps are valuable for their properties
solubilization detergency dispersion emulsification and corrosion
Their principal use is in lubricating oils for sludge dispersion
solubilization of water and corrosion inhibition. They are also widely
other products for corrosion inhibition and emulsification.
hydrocarbon sulfonates are the surfactant components in both product
green soaps contain a higher proportion of disulfonates than the
sulfonates which are principally monosul fonates.
ethyl hexyl) sulfosuccinate is the largest volume product of this
group. It is
now a widely used specialty surfactant.These sulfosuccinates as sodium
are available as white waxy odourless solids or as concentrated
solutions. The di C8 esters have the optimum solubility balance for use
water or aqueous solution with low inorganic salt content lower alkyl
are more effective in saline solutions. Sodium dialkyl sulfosuccinates
highly surface active but the susceptibility of the ester linkage to
alkaline hydrolysis limits their usefulness. The products have strong
penetration and solubilization properties. The symmetrical diesters are
produced by esterification of maleic anhydride using conventional
followed by addition of sodium bisulfite across the olefin linkage.
specialty surfactants make up the widely used but relatively low volume
naphthalene sulfonate products viz. salts of alkylnaph thalene
of sulfonated formaldehyde naphthalene condensates salts of naphthalene
sulfonates and salts of tetrahydronaphalene sulfonates.
concentrated dry form most of the salts are almost odourless light grey
They are readily and highly soluble in water. In fact except for the
derivatives the naphthalene sulfonates are generally too soluble to be
surface active in soft water. The naphthalene sulfonates are stable to
hydrolysis in acidic or alkaline media and are not sensitive to
strong oxidizing agents under use conditions.
sulfonates are used in many different applications as wetting and
agents. Several members of the series are effective as stabilizing and
suspending agents in disperse systems. Some of the products are useful
their solubilizing properties. Hard water does not adversely affect the
activity of typical members of the series.
N acyl N alkyl taurates
technically interesting as the only class of anionic surfactants with
combination of many advantages. They are stable against hydrolysis by
alkaline media at use concentrations. They show no loss of performance
water. They have soap like biodegradability and residual feel on washed
and they have a molecular structure capable of yielding either strong
or strong detergent configurations. For example the products RCON (R`)
CH2CH2SO3Na are strong detergents when R = C11 C17 and R` = CH3 or C2H5
strong wetters when R = R` = C6 9. Relatively high raw material costs
usage of the presently available N acyl N alkyl taurates in the
category and have precluded the introduction of additional products
markedly different properties.
commercial product N Oleoyl N
methyltaurate is marketed as a light yellow solid at about 70 per cent
at lower concentrations in water as a light coloured slurry solution or
is principally used in detergent applications with out builders.
Foaming of the
N methyl derivatives is only moderate and is not readily improved by
foam builders the N cyclohexyl derivatives are low foaming detergents
of sodium N oleoyl N methyltaurate involves three chemical steps and
average 95 percent or higher in each step.
2 Sulfoethyl Esters of Fatty Acids
commercially as b sulfoesters resemble closely in properties the fatty
from which they are derived but they have the advantage that hard water
not impair their performance. Only the sensitivity of the ester linkage
hydrolysis has prevented their widespread usage in consumer detergents.
Hydrolysis is not a problem with detergents for personal use and the
salt of the 2 sulfoethyl ester of lauric acid or similar coconut acid
found acceptance as the foaming and cleansing ingredient in synthetic
bars. The oleic acid analog is less foaming but is a good detergent
specialty uses in neutral or mildly alkaline systems.
be produced commercially from isethionate (obtained by the reaction of
oxide with a concentrated solution of sodium bisulfite) and the fatty
acyl chloride. The reaction between the acyl chloride which is a
and the powdered anhydrous sodium isethionate is carried out in the
water or solvent under vacuum in a heavy duty mixer. After the total
added to the reactor and brought to temperature HCL is rapidly evolved
the finally divided light coloured product as the sodium salt.
increasing availability of relatively low cost linear 1 olefins in the
C18 range has spurred research and commercial development of their
The 3 and 4
hydroxysulfonates which may amount to as much as half of the yield of
sulfonated products are not very water soluble but they are solubilized
presence of the more soluble olefin sulfonate. The sulfonation mixture
referred to as a olefin sulfonate or AOS has detergency and foaming
similar to C11 14 LAS. It is superior in performance to similar
from internal straight chain olefins. Biodegradability of the AOS is
better than LAS toxicity and skin irritation are slightly less.
Sulfates & Sulfated Products
group in the surfactants falling in this group is SO3 attached through
oxygen atom to a carbon atom in the hydrophobic moiety. The additional
makes the sulfate a stronger solubilizing group than the sulfonate but
the C O
S linkage of the sulfates is more easily hydrolyzed than the C S
linkage of the
sulfonates. This susceptibility to hydrolysis especially in acidic
the utility of the sulfates. Solubilization of hydrophobes through the
combination of ethoxylation and sulfation is frequently used to obtain
optimum solubility balance and also to utilize less expensive raw
that cannot be solubilized sufficiently by sulfation alone e.g. derived
tallow alcohols. The shift of the detergent industry to more
products has started a trend away from ethoxylated and sulfated alkyl
and towards ethoxylated and sulfated aliphatic alcohols. The principal
groups of this class of surfactants are discussed below.
Alkyl Sulfates (Sulfated Alcohols)
of this class of surfactants are obtained by reduction of fatty acids
of C12 to C20 hydrocarbon groups.
olefins sulfates are prepared by the addition of sulfuric acid to an
products have been marketed under the Teepol trademark of shell Oil
Sulfates obtained from the normal primary alcohols are similar in
properties and in feel or emollient characteristics to the soaps of
corresponding molecular weight. The branched chain alkyl sulfates are
wetters. As the carbon chain length increases the temperature needed to
maximum detergent and wetting effects also increases. The stability of
sulfates to hard water is excellent. In fact magnesium lauryl sulfate
voluminous foams with a low water content that is useful in rug
the soil is removed by vacuum pick up of the foam that is generated by
brushing with a minimum volume of detergent solution. Sensitivity to
in hot alkaline or acidic media is one of the principal disadvantages
alkyl sulfates. Alkyl sulfates are high foaming detergents and strong
as well as effective emulsifiers and dispersants. Some of the products
as leathering and cleansing agents in shampoos and dentifrices. Others
detergent and wetting agents for textile processing. Another use of the
sulfates is as emulsifiers and dispersents in emulsion polymerization.
can be prepared as the ammonium sodium potassium magnesium
triethanolamine salts which is indicative of the marked influence of
cations on the performance properties of this series of anionic
Sulfated Natural Fats and Oils
surfactants from natural fats and oils are obtained by the reaction of
acid which either CH = CH or OH groups in natural fats and oils. The
half esters so obtained are neutralized with caustic soda in a later
the first oil to be sulfated to obtain a commercial surfactant other
Later on almost every potentially available animal vegetable and fish
tried and it was found that ricinoleic acid which contains one hydroxyl
and one double bond is a desirable constituent of an oil for sulfation.
acid is also satisfactory. Esters of these acids can usually be
sulfated with a
minimum of hydrolysis. Polyunsaturated fatty acid moieties are
components of glycerides for sulfation since the resulting surfactants
usually dark in colour and sensitive to oxidation.
NON IONIC Surfactants
A non ionic
surfactant as the name implies bears essentially no charge when
dispersed in aqueous media. The hydrophilic tendency in a non ionic is
primarily to oxygen in the molecule which hydrates by hydrogen bonding
molecules. The strongest hydrophilic moieties in non ionics are ether
and hydroxyl groups but ester and amide linkages which are also
present in many non ionics. The contribution of each oxygen to
is weak and non ionic molecules must contain a multiplicity of them in
be water soluble. Nearly all of the unmodified polyol surfactants are
lipophilic and they are frequently used as coemulsifiers in
more hydrophilic surfactants. One advantage of the non ionics is that
compatible with ionic and amphoteric surfactants. Polyoxyethylene
solubilization is the key to the substantial and continuing growth of
ionics. Since the polyoxyethylene group can be introduced into almost
organic compound that has reactive hydrogen a wide range of organic
can be solubilized by ethoxylation. Sub division of the non ionics into
in accordance with the composition of the solubilizing groups is not as
straight forward as with the ionic surfactants.
polyoxyethylene solubilized non ionics are mainly used as textile
The solubility of these products depends on recurring ether linkages in
polyoxyethylene chain. A solubilized molecule contains many such chains
hydrophilic tendency increases with the polyoxyethylene content of the
and 60 70 per cent by weight is required on most surfactant hydrophobes
complete miscibility with water at room temperature. A rule of thumb is
the hydrophilic strength of one ethylene oxide unit is approximately
the hydrophobic strength of one methylene unit. The water solubility of
polyoxyethylene compounds decreases as the temperature increases which
attributed to a decrease in the degree of hydration or to an increase
size of the micelles. The temperature at which a second phase appears
the cloud point a practical solubility test that is not sensitive to
concentration differences in the range between 0.5 to 10 per cent by
minor proportion of anionic mixed with a non ionic will often raise the
point to several degrees. Surface activity and performance efficiency
polyoxyethylene non ionics is not adversely affected by hard water.
electrolyte concentrations in which sodium ions are the predominant
decrease the solubility of polyoxyethylene compounds by a salting out
hydrochloric acid and calcium ions increase their solubility. Non ionic
surfactants solubilize iodine in aqueous solutions and lessen its
humans but do not weaken its biocidal activity
to the lower
forms of life. The polyoxyethylene surfactants are moderate foamers and
respond to the conventional foam boosters. They exhibit a foam maximum
function of polyoxyethylene content. Low foaming non ionics are
terminating the polyoxyethylene chain with a less soluble group e.g.
oxide. A significant advantage of solubilization by means of
the capacity of attaining almost any hydrophilic/hydrophobic balance. A
shortcoming is that the polyoxyethylene non ionics tends to be liquids
melting waxes that are difficult to incorporate into dry free flowing
Flaked solid products containing a high ratio of polyoxyethylene are
manufactured but their surface activity is low because they are too
of an aliphatic alcohol alkyl phenol or fatty acid into a
derivative can be divided into two steps addition of ethylene oxide to
hydrophobe to form a monoadduct and subsequent additions of ethylene
oxide in a
polymerization reaction. Ethoxylations of these hydrophobes are
bases. Ethoxylation is normally carried out as a batch re action
continuous reactors have been designed and operated. The hydrophobe and
solution of catalyst are charged into a reactor. Air and solvent for
catalyst are removed by agitating and heating under a vacuum or purging
nitrogen or both. When the hydropbobe is at the reaction temperature
of ethylene oxide is started. The polymerization is exothermic (20
ethylene oxide reacted) and the rate of ethylene oxide addition should
exceed the cooling capacity of the reactor since careful maintenance of
temperature is essential for reproducible manufacture of products to
specifications. The end point of ethylene oxide addition is often
testing the solubility of a sample for its cloud point in water a salt
or a water solvent mixture. After the reaction is complete the catalyst
and the product is discharged to storage or packaged. Polyoxyethylene
solubilized non ionics are poly disperse mixtures of compounds that
principally in the distribution of the polymer chain lengths. Their
usually approximate those of the pure isomer represented by their
Ethoxylated Alkyl Phenols
polyoxyethylated C8 to C12 alkyl phenols have a slight aromatic odour
from pale yellow to almost colourless. Products with low
content are liquids and their viscosity increases with the content of
ethylene oxide. High ratios of polyoxyethylene to hydrophobe are waxes.
specific gravity at room temperature increases with polyoxyethylene
from less than 1 to 1.2 Physical properties of the polyoxyethylated
alkyl phenols e.g. dinonylphenol and hexadecylphenol are similar to
the C8 to C12 derivatives with the same wt. percentage of combined
in water of the ethoxylated alkyl phenols increases with the
content. About 60 per cent by weight of polyoxyethylene is required for
complete miscibility in cold water and at above 75 per cent of
the products do not cloud out at the boiling point. Water hardness does
adversely affect the surface activity of the products. The solubility
polyoxyethylene alkyl phenols in highly aliphatic mineral oils
with increasing polyoxyethylene content than the corresponding increase
solubility in water. Solubility in aromatic solvents and unsaturated
triglycerides persists at higher mole ratios of combined ethylene oxide
hydrophobe. The excellent stability of the polyoxyethylene alkyl
against decomposition is demonstrated by their uses in formulations for
cleaning of metals in hot alkaline detergent systems and in oil well
fluids for use at high bottom hole temperatures.
surface activity of the unformulated polyoxyethylene alkyl phenols in
hardness of 0 300 ppm is associated with polyoxyethylene proportions in
range of 50 75. per cent by wt. The optimum composition varies somewhat
range depending upon the property. Typical commercial products of
polyoxyethylene alkyl phenols include nonyl octyl and doceyl phenoxy
polyethylene oxy ethanols. Uses of polyxyethylene alkyl phenols as a
of polyoxyethylene content can be summarized as follows
phenols containing 20 40 per cent polyoxyethylene are used as defbamers
surfactant solutions detergent and/or dispersing agents in petroleum
intermediates for sulfation.
phenols containing 40 60
percent polyoxyethylene are used for oil soluble detergents dispersants
emulsifiers emulsifiers in emulsifiable concentrates of insecticides
herbicides intermediates for sulfation.
phenols containing 60 70 per cent polyoxyethylene are used for textile
detergents and processing auxiliaries pitch control in manufacture of
pulp rewetting agents in paper towels processing assistants in leather
manufacture detergents in industrial and consumer cleaning products
agents in acid and alkaline cleaners emulsifiers in emulsifiable
of insecticides and herbicides.
phenols containing 70 80 per cent poly oxyethylene are used for
wetters at high temperature and/or electrolyte concentrations
fats oils and waxes stabilizers for synthetic latexes wetting and
agents in caustic solutions.
phenols containing 80 95
per cent poly oxyethylene are used as stabilizers synthetic latexes
for vinyl acetate and acrylate emulsion polymerization dyeing and
assistants lime soap dispersants.
ethoxylations of Alkyl phenols are always alkali catalyzed but the
conditions catalyst and catalyst concentration are chosen to obtain
properties for the intended use. All of the Alkyl phenol combines with
molecule of ethylene oxide to form the monoadduct before the build up
polyoxyethylene chains start but by relatively minor variations in
conditions it is possible to obtain either a broad or narrow
isomers at the same percentage content of polyoxyethylene. These
are reflected in the properties of the products particularly the
Another variant at constant gross composition is the percentage of
in the product i.e. ethylene oxide polymer not combined with the Alkyl
Ethoxylated Aliphatic Alcohols
aliphatic alcohols are costlier than the ethoxylated Alkyl phenols but
recent change over to biodegradable products in the ensuing
industrial and consumer products a shift in non ionic types appears to
taking place with polyoxyethylene alcohols instead of polyoxyethylene
Alkyl phenols replacing the branched chain Alkyl phenol derivatives in
significant fraction of the newer formulations. In the products of
which include oleyl cetyl
stearyl lauryl tridecyl
myristyl and tallow
polyethylene oxy ethanols the
hydrophobes are generally mixtures of straight chain alcohols in the
C12 to C18 and contain combined ethylene oxide in more ratios varying
from 1 to
50 to hydrophobe. The undiluted products vary in physical form from
many solids viscosity in each homologous series increases as the
polyoxyethylene content increases. The products have a slight odour
characteristic of the hydrophobe that decreases as the polyethelene
increases. The liquids vary from pale yellow to almost colourless and
solids from yellow to white waxes the products become lighter coloured
polyoxyethylene content increases. Within each homologous series the
gravity at room temperature increases with the polyoxyethylene content
slightly less than 1 until it levels off a little under 1.2. Solubility
alkylpoly (ethyleneoxy) ethanols in water increases with the ethylene
content about 65 70 vol percent of polyethylene is required for
miscibility at room temperature. The
solubility of the polyoxyethylene derivatives of straight chain
aliphatic solvents is slightly greater than for the Alkyl phenols of
polyoxyethylene content. The water hardness does not impair the surface
activity of the alkylpoly (ethyleneoxy) ethanols.
properties and uses of the polyoxyethylene alcohols parallel very
of the polyoxyethylene Alkyl phenols. The usage of alkylpoly
ethanols is divided more evenly among the available hydrophobes than
phenols. This makes available a wider range of solubilities in water
liquids and contributes to the widespread use of the products as
purpose emulsifiers. The Alkyl polyethyleneoxy ethanols have certain
as textile fibre lubrication that are due to properties of the
for which the comparable polyoxyethylene Alkyl phenols are not
processes and equipment for manufacture of the alkylpoly (ethyleneoxy)
are similar to those described for the Alkyl phenols. However the rate
reaction of primary alcohols with ethylene oxide is much faster than it
Alkyl phenols it is much closer to the rate at which the
grows. Thus the build up of polyoxyethylene polymer chain starts before
the hydrophobe has reacted with one unit of ethylene oxide. The
alcohols with ethylene oxide varies in the order primary >
tertiary. It is difficult to prepare polyoxyethylene derivatives of
alcohols by direct reaction of the alcohol with ethylene oxide.
esters may be polyolsolubilized or poly oxyethylene solubilized or both
surfactant use. They are based on several different types of
accordingly they are classified as glycerol esters polyethylene glycol
esters ethoxylated nhydrosorbitol esters ethylene a and diethylene
esters propanediol esters ethoxylated natural fats and oils carboxylic
esters silicone compounds etc.
partial fatty acid esters either mono or diglycerides of fatty acids.
products of commerce are almost invariably mixtures of mono and
that also differ in respect to the positions of the hydroxyl group that
esterified. Typical products in the series include the mono and
stearic lauric oleic and ricinoleic acids and coconut tallow lard
and safflower oils.
Mono and di
glycerol esters of the saturated fatty acids are light coloured solids
melting points between 25 and 85°C. The 1 monoglycerides have higher
points than the corresponding 2 monoglycerides. The glycerides of the
unsaturated fatty acids are liquids at room temperature. The partial
fatty esters have the characteristic odour of the fats from which they
derived. The polyol group of a monoglyceride is not strong enough as a
moiety to carry even an easily solubilized acid like oleic into aqueous
solution. Despite their lack of water solubility the partial glycerol
have commercially important and technically interesting surfactant uses.
The uses of
and diglycerides centre around applications involving emulsification
suspension solubilization and lubrication. One important use is as
foods and pharmaceuticals. Products intended for ingestion are prepared
edible fats. Mono and di glycerides are widely used in bread cakes and
bakery products for their emulsifying dispersing and lubricating
They are also used in candies ice creams yeasts butter whipped tappings
icings. Flavour oils for carbonated beverages as well as bakery
emulsified or solubilized by surfactant mixtures that include blends of
diglycerides. Glycerol mono stearate is used as an emulsifier and
cosmetic formulations. The partial glycerol esters are used as
compounds of textile
mill processing and in lubricants and softener formulations. The
find application as emulsifiers lubricants and corrosion inhibitors in
and finishing of metal products. In the manufacture of paints and
mono and diglycerides are used as emulsifiers dispersants suspending
fats with glycerol is the most important industrial method for the
of the partial fatty acid esters of glycerol. In this reaction the
groups are redistributed between the original combined glycerol and the
glycerol without weight loss by heating at 180 250°C in the presence of
Polyethylene Glycol Esters
ethylene esters of fatty acids and of aliphatic carboxylic acids
abietic acid comprise the polyethylene glycol series of surfactants.
and uses of these two groups of products differ markedly. Commercial
polyoxyethylene fatty acid esters are mixtures that contain varying
of mono esters di esters and polyglycol. The composition of the mixture
forced toward the mono or di ester by the ratio of reactants and
manufacture. The polyoxyethylene esters of fatty acids range in
from free flowing liquids to slurries to firm waxes.
homologous series the products change from liquids to waxes as the
content increases. Only low mole ratios of polyoxyethylene to
acids or lower molecular weight acids yield liquid products. The odour
products is characteristic of the fatty acid hydrophobe and decreases
polyoxyethylene content increases. Odour and odour stability are
characteristics of these products because of their use in textile
Colour stability is also important for the same reason. The oleates for
have good softening and lubricating properties but are precluded from
because of yellowing on exposure to air and heat.
linkage is slightly hydrophilic and only about 60 wt. per cent of
polyoxyethylene is required to solubilize the saturated fatty acids in
room temperature. The surface activity of the fatty acid polyglycol
wetting and surface tension lowering is in the useful range but less
ethoxylated Alkyl phenols or aliphatic alcohols. The products are low
in aqueous solutions which is advantageous for certain uses.
a key property of this series of compounds and its importance is
the wide range of lipophilic solubilities that are available in
products. Susceptibility to hydrolysis in hot acidic or alkaline
their principal limitation. The fatty acid that is formed by acidic
either separates as oil or forms an insoluble precipitate with the
ions in hard water.
Polyoxyethylene fatty acids
are used extensively in the textile industry as emulsifiers for
antistatic agents softeners fibre lubricants and detergents for neutral
operations. The products are also used as emulsifiers in cosmetic
used commercially for manufacture of the polyoxyethylene acids. One is
alkali catalyst reaction of a fatty acid with ethylene oxide. The other
esterification of a fatty acid with a preformed polyethylene glycol in
presence of an acid catalyst. Some manufacturers claim that the
different for products of the same gross composition as prepared by the
However the ethoxylation catalysts also catalyze trans esterification
products of direct ethoxylation approach closely those obtained by
esterification if the manufacturing process is directed to this end.
Deodourization and decolorization treatments are commonly incorporated
polyoxyethylene derivatives of the rosin acids are generally similar to
corresponding polyoxyethylene fatty acids in surfactant properties and
processes of manufacture except that they are stable towards
chemical stability of the polyoxyethylene tallates together with their
characteristic low foam generation at use concentrations makes
components of consumer deter include the mono and diglycerides of
oleic and ricinoleic acids and coconut tallow lard cottonseed and
Mono and di
glycerol esters of the saturated fatty acids are light coloured solids
melting points between 25 and 85°C. The 1 monoglycerides have higher
than the corresponding 2 monoglycerides. The glycerides of the
fatty acids are liquids at room temperature. The partial glycerol fatty
have the characteristic odour of the fats from which they are derived.
polyol group of a monoglyceride is not strong enough as a hydrophilic
carry even an easily solubilized acid like oleic into aqueous solution.
their lack of water solubility the partial glycerol esters have
important and technically interesting surfactant uses. The uses of mono
diglycerides centre around applications involving emulsification
solubilization and lubrication. One important use is as additives to
pharmaceuticals. Products intended for ingestion are prepared from
Mono and di glycerides are widely used in bread cakes and other bakery
for their emulsifying dispersing and lubricating properties. They are
in candies ice creams yeasts butter whipped tapings and icings. Flavour
for carbonated beverages as well as bakery products are emulsified or
solubilized by surfactant mixtures that include blends of mono and
diglycerides. Glycerol mono stearate is used as an emulsifier and
cosmetic formulations. The partial glycerol esters are used as
textile mill processing and in lubricants and softener formulations.
products also find application as emulsifiers lubricants and corrosion
inhibitors in cutting drawing and finishing of metal products. In the
manufacture of paints and polymers the mono and diglycerides are used
emulsifiers dispersants suspending agents and grinding oils.
fats with glycerol is the most important industrial method for the
of the partial fatty acid esters of glycerol. In this reaction the
groups are redistributed between the original combined glycerol and the
glycerol without weight loss by heating at 180 250°C in the presence of
esters of anhydrosorbitol are the second largest class of polyol
surfactants. The important commercial products in the group are mono di or triesters of sorbitan
and fatty acids.
Sorbitan is a mixture of anhydrosorbitols with the principal isomers
being 1 4
sorbitan and isosorbide.
oleates and the monolaurate are pale yellow liquids. The palmitates and
stearates are light tan solids. Sorbitan is not a strong hydrophilic
its derivatives are not water soluble but they are soluble in a wide
mineral and vegetable oils. The sorbitan esters are lipophilic
softeners and fibre lubricants. Many of the products have been approved
human ingestion and are widely used as emulsifiers and solubilizers in
and pharmaceuticals. Another important application is in synthetic
manufacture and textile processing as antistats fibre lubricants
emulsifiers of textile mill processing oils. The sorbitan esters are
widely used as emulsifiers in cosmetic products.
anhydrosorbitol esters are prepared commercially by direct
sorbitol with a fatty acid in the presence of an acidic catalyst at
temperatures in the range 225 250 °C. Internal ether formation as well
esterification takes place under these conditions. The commercial
importance in this group include the mono and trilaurates oleates
Ethoxylated Anhydrosorbitol Esters
the sorbitan fatty acid esters leads to a series of more hydrophilic
surfactants. They are widely used as emulsifiers antistats softeners
lubricants and solubilizers. The ethoxylated sorbitan esters are often
co emulsifiers with the unethoxylated sorbitan fatty acid esters or the
glycerol partial fatty acid esters. Sorbitan fatty acid esters can be
with ethylene oxide in the presence of an alkaline catalyst at
from 130 to 170°C to produce the ethoxylated derivatives.
Glycol Esters of Fatty Acids
glycol diethylene glycol and 1 2 propanediol esters of fatty acids are
used surfactants. The commercial products are mixtures of mono and
even though the stated composition usually refers only to the principal
component. The mono and dilaurates and oleates of ethyleneglycol
glycol and propylene glycol are liquids. Stearates of these glycols are
The glycol esters are strongly lipophilic emulsifiers opacifiers and
plasticizers that are normally formulated in combination with
emulsifiers. They are used as components of cosmetic preparations. The
monoesters of glycols can be manufactured by the alkali catalyzed
ethylene or propylene oxide with fatty acids. Mono and diesters are
prepared by esterification of a fatty acid with a glycol.
Ethoxylated Natural Fats Oils and Waxes
commercial importance in this group of surfactants are chiefly
castor oil and ethoxylated lanolin derivatives.
triglyceride with a high content of esterified ricinoleic acid. Its
ethoxylation in the presence of an alkaline catalyst to a
content of 60 70 wt. per cent yields water soluble surfactants. The
of the ethoxylated derivatives is more complex than might be expected.
ethoxylates are yellow to amber viscous liquids with specific gravities
slightly greater than 1.0 at room temperature. Ethoxylated castor oils
hydrophilic emulsifiers dispersants and lubricants. They are used as
assistants and finishing agents in the manufacture of paper leather and
products. Other uses are in emulsion polymerizations paints polishes
cosmetic products. Skin irritation and phytotoxicity are usually low.
are derived from the fat that is stripped from raw wool. They are a
cholesterol isocholesterol and other higher alcohols. Lanolin alcohols
by bleaching solvent extraction crystallization or molecular
ethoxylated to yield non ionic emulsifiers. The mole ratios of ethylene
to alcohols that are offered commercially represent a full series of
and hydrophilic products. Their largest use is as emulsifiers in
days of textile industry soap in one form or the other was the only
emulsifying and dispersing agent available. Its inability to stand hard
and acid led to the development of a product possessing the valuable
of soap without its defects. The first successful attempt towards this
Fremy a Frenchman who studied the effect of concentrated sulfuric acid
oil but it was A. Runge who first prepared sulfated olive oil by first
the olive oil with concentrated sulfuric acid and then neutralized the
product with cold caustic potash solution. The product was an oily
dispersible substance. A British patent was granted to Mercer in 1847
sulfonating olive oil which was to be used in dyeing madder Turkey
then many different oils have been sulfated e.g. rapeseed oil
cottonseed oil castor
oil groundnut oil and corn oil etc and neutralized with alkalies. The
Turkey Red Oil has since been used for sulfonated castor oil.
between any oil and sulfuric acid takes place in several ways depending
temperature the intimacy with which the materials are brought into
the time. The major reaction results in a sulfated rather than a
product. With ordinary oils sulfation occurs at the double bonds of the
acids resulting in triolein hydrogen sulfate. Sulfuric acid reacts with
hydroxyl group of the ricinoleyl (12 hydroxy 9 octadecenoic acid)
castor oil to form the sulfate.
when used in the last stage of wet processing of textiles impart the
desirable softness or fullness and thus by the end of the 19th century
of sulfated oils as an important textile auxiliary chemical and
became well established. The sulfated oils of the late nineteenth
usually only partially sulfated and thus contained a proportion of
fatty glycerides. Sulfated oils in which a large part of the glycerides
been hydrolysed to the fatty acids possessed all the faults of the
themselves particularly their sensitivity to hard water and to acidic
conditions. These defects led to the production (in the 1920 35 period)
called highly sulfonated oils.
Chemistry of Sulfation and Sulfonation
oils the strongly polar sulfo group appears in the centre or
thereabouts of a
C18 alkyl chain and the specific properties of the products although
not so highly developed as in compounds in which the polar group
long alkyl or acyl carbon chain. Hence for many purposes the sulfonated
being replaced by one or other of the more recent preparations.
not been sulfonated but sulfated and the term sulfonated oil does not
accurate picture of the process. Other side reactions proceed
during either of the above two main actions. The sulfate group is
removed in an acid medium in presence of moisture and consequently the
product contains a certain proportion of hydroxy acids. Further estolides and possibly other
compounds are produced during the reaction by elimination of water
alcoholic group of one molecule of sulfated fatty acid and the carboxyl
possibly sulfate) groups of another. Finally in the case of sulfation
of oils the
sulfated derivatives have the typical constitution of fat splitting
(hydrolytic) agents and considerable production of free fatty acid
otherwise from neutral oil usually takes place during their manufacture.
hand production of true sulfonic derivatives in place of or
sulfated products may occur if the action is allowed to take place
strongly dehydrating conditions and especially if fuming sulfuric acid
trioxide or chlorosulfonic acid is used in place of sulfuric acid as
sulfonating agent. In these cases the reaction probably takes a course
such as the
acid sulfate group in the complex formed is comparatively easily
during subsequent washing of the product with water and true (hydroxy)
acids CH (SO3H) CH (OH) and their condensation products are present in
material finally obtained. These compounds will of course be completely
in so far as the direct attachment of the sulfonic group SO3H to a carbon atom is
concerned whereas the
hydrogen sulfate groups of turkey red and the ordinary sulfonated oils
oleins are liable to hydrolyse in presence of water of dilute acid
free sulfuric acid and a neutral hydroxy fatty compound as between the true fatty
and the unhydrolysed sulfate derivatives of the type of turkey red oil
probably little to choose on the score of relative efficiency. Claims
true sulfonates are more effective textile assistants may in reality be
upon their greater stability which is due to their incapacity to loose
polar sulfo acid group by hydrolytic action.
Applications of Sulfonated Oils
and fats fulfill many vital needs in the textile processing industry.
earliest use as assistants in the dyeing of fabrics still remains one
dominant functions in this field. They are characterized by their
properties surface activity and colloidal nature. These characteristics
them admirably to the dyeing process. Sulfated castor oil is used in
cotton and rayon fabrics with direct dyeing colours to facilitate
and ensure level dyeing. It is also used as dispersing and penetrating
the application of vat and naphthol colours. Sulfated oil containing
organically combined sulfate contents (5 to 7 percent) is most suitable
these uses as they generally possess greater penetrating power and
tolerance to electrolyte. Excessive sulfation however reduces the
properties of sulfated oils and destroys the natural antioxidant which
prevent rancidity. For this reason finishing oils should be prepared to
a minimum amount of organically combined sulfate consistent with good
solubility and stability.
and fats are probably consumed in greater quantities in finishing
Here they are incorporated into the fabric in the final wet process for
purpose of enhancing its appearance and feel. Sulfated olive oil is now
universally used as a softener on cotton and rayon fabrics where
silkiness and drape are desired. Sulfated olive and castor oils are
lubricants for soaping and as tinting oil ingredients for natural silk
rayon. In both cases the sulfated oil is generally combined with
dispersed in water as is the case when they are used in warp sizing
formulation. Sulfated oils are sometimes combined with highly purified
oils to impart added surface lubrication and sleekness to the fabric.
is commonly used for moderate softening effects and to add body or
weight to the fabric. For additional body and firmness the sulfated
sometimes combined with gums and starches. They may also be combined
polyoxyethylene condensate and salt or an alkylolamide condensate and
for the dual purpose of scouring and fulling of woollen fabrics.
tallow has proved to be an excellent emulsifying agent with all types
and thus it has been possible to formulate many types of wax emulsions
sulfated tallow. These wax emulsions are applied to cotton and rayon to
an effect of fullness and body enhancing the lustre of calendared
One of the
greatest uses of sulfated tallow is in the warp sizing of cotton yarns
is generally used in conjunction with gums or starches. Here it serves
function of plasticizing the size film and lubricating the yarn to
frictional resistance in the loom. Mixtures of sulfated oils with white
oils impart excellent softness and lubrication and are quite commonly
high quality cotton rayon fabrics. The presence of high grade mineral
improves materially the heat and ageing stability of sulfated finishing
and cresylic acid are mixed with sulfated oils to improve their
detergency power. They are then used as kier boiling assistants general
scouring agents and agents for removal of grease and tar stains.
Manufacture of Sulfonated Oils
sulfated with concentrated sulfuric acid and sulfonated with sulfur
Both processes are of semi batch type and the sulfur trioxide process
product containing a much higher combined SO3.
sulfation is carried out in a
lead lined vessel jacketed or fitted with cooling coils and agitator.
reactor is fed with appropriate amounts of the oil and about 25 to 50
on the basis of the amount of oil charged cold and concentrated
is added to the oil with constant stirring. The circulation of cooling
started simultaneously. The rate of addition of acid must be so
the temperature does not exceed 35°C. With olive or rapeseed a some
temperature is safer and the less saturated oil e.g. fish linseed
are better treated at or below 10°C to avoid undesirable results. After
addition of all the acid cooling and agitation are continued for some
in order to complete the reaction. The mixture is left overnight and
stirred next day. The reaction is considered complete when a sample of
product completely solubilizes in a given amount of water depending
degree of sulfation desired.
acid is removed by adding a quantity of cold water equal in weight to
reaction mixture and allowing it to settle overnight. The aqueous acid
then drawn off and the oil is either washed several times with sodium
solution or treated with dilute caustic soda solution until the mixture
neutral to Congo red paper. Exacting control during washing and
step is essential. Conditions occur during this operation which tends
promote desulfation and hydrolysis resulting in an end product low in
sulfur trioxide and high in free fatty acids. When it is desired to
splitting to the greatest possible extent washing is done with sodium
solution instead of salt solution. Washing and neutralization
kept low time of reaction short and pH adjustment accurate. After
neutralization the oil is allowed to settle out from the excess of the
of inorganic salts. The finished product usually contains about 35 per
water. Optimum conditions for individual oil should be determined by
experiments. Monel and nickel clad steel are excellent materials of
construction for the reactor but since they are costly lead lined steel
development work for sulfonation with SO3 was
carried out by flask sulfonation. In a typical laboratory batch
oil is charged to a reaction flask and SO3
diluted to 4 per cent by
volume with dry air is introduced below the surface while agitating
The reaction temperature is maintained between 45 50°C and the reaction
between 20 25 minutes. After all of the SO3 has
been added the
reaction mass is drowned in 15 per cent sodium hydroxide. The resulting
contains about 25 percent water and has 8 per cent organically combined
based on 100 per cent solids. It also displays excellent water
in the laboratory sulfonation can generally be duplicated in the pilot
product quality is often improved because of better heat removal and
distribution in the continuous reactor. The continuous reactor used for
work consists of a set of vertically mounted water jacketed stainless
concentric cylinders divided into three sections the distribution
reaction section and the separation section. The main function of the
distribution section is to direct flow so as to deposit continuously an
film of oil to the inner and outer walls of the reaction section. This
by pumping the castor oil through small peripheral shots in the
mixture is introduced above the distributor and passes through the
space between the concentric cylinders in such a way that contact is
made with the
castor oil just at the point where the film is developed. In the upper
the reaction section the gas stream containing the initial
concentration of SO3
contacts the unreacted castor oil. As the gas stream and
the organic film
continue to move together down the reactor waIls SO3
is absorbed by
the liquid organic phase reacting with it so that at the end of the
section SO3 remaining in the gas phase
concentration. Virtually all the SO3 in the
entering gas stream is
absorbed by the organic film and converted to organic sulfate or
film is in intimate contact with the water jacketed reactor walls and
in the liquid film generated by differential velocity of the gas stream
provides an efficient heat removal and excellent temperature control.
minimizes localized overheating. The reaction mass then passes into the
separation section where acid product is withdrawn for subsequent
and spent gas is separated and exhausted to atmosphere through a
A batch SO3/air
system on the other hand would operate in a manner similar to that used
continuous system except that the continuous reactor would be replaced
stainless steel reaction vessel equipped with a turbine agitator and
circulating pump and a heat exchanger.
India sulfuric acid is
generally used for sulfation of oils and thus most of the products
sulfated oils rather than sulfonated oils although they are marketed
latter name. They contain about 30 50 and 75 percent sulfated organic
and free oil the rest is mainly water.
Sulfation of Individual Oils
at one time manufactured according to a German process as practiced by
Felt Chemie. The product was marketed as A Virol K M. In this process
sulfuric acid is slowly added into 1600 kg. castor oil with continuous
in about four and a half hours. The temperature of the mixture is
between 25 30°C by circulating water in cooling coils and/or jacket.
stirring for 1½ hour further 130 kg. of sulfuric acid is added slowly
continuous stirring in over 3 hours and the batch is allowed to stand
hours without stirring. Finally a further quantity 50 kg. of sulfuric
added in about 1 hour and stirring is continued for another hour. The
then neutralized as quickly as possible by stirring with 40°Be caustic
(860 kg.). The temperature rises 90 to 100°C. The product should now
acid reaction to phenolphthalein. Live steam is now passed in for 1/2
After standing overnight the aqueous salt layer is run off. The product
settled for 2 weeks the aqueous layer is run off and it is then
addition of requisite quantity of water.
are condensates of
alkylolamines and fatty acids and are generally referred to as foam
additives. Their use in detergent formulation goes a long way towards
the problems of stabilization improvement and creaming of lather which
important to the success of compounded detergents. They can be used as
detergents in their own right but probably their main outlet is as
in shampoo and liquid and powder detergent production.
of commercial interest can be divided into three classes
from the reaction of one
mole of a monoalkylolamine and one mole of fatty acid.
of reaction of one mole of a dialkylolamine with one mole of fatty acid.
products of more
than one mole of a dialkylolamine with one mole of fatty acid.
products of the class (1) with free fatty acid contents in the range of
per cent are oily light brown liquids which are soluble in water and
good detergents particularly for cleaning hard surfaces walls tiles
These products can be used in the formulation of liquid cleaners and
following formula has been suggested.
formulation is advocated for packing in mild steel drums for sale to
the class (2) with low free fatty acid contents are used as foam
in the formulation of liquid cleaners. They also act as solubilizing
alkyaryl sulfonates and sodium lauryl sulfates depressing the cloud
mixtures and helping to ensure that no separation of active matter
low temperatures. These products are also used to a more limited extent
additives for powder detergents they are incorporated by spraying in
state on to spray dried or physically mixed powders.
monoalkylolamine derivatives find their major outlet as builders for
purpose spray dried powder detergents where they are normally used at
of 1 3 per cent. The range of useful additives is wide but can be
some extent by economic considerations. In the choice of additive for
particular formulation the following points must be considered
the additive have the desired foam boosting properties when added at
economic level ?
the raw materials available at a reasonable and stable price?
the additive be made
consistently or does it suffer batch to batch variation which impairs
Is it compatible with other
ingredients in formula e.g. if used with a liquid product can it be
sufficiently solubilized together with the other solution ?
Can it be easily incorporated
at the right concentration in the powder e.g. can it be sprayed evenly
the powder will it be stable at spray drying temperatures or will it
a sticky powder and tend to bleed out ?
Is it stable under long term
storage conditions or will it turn rancid or affect the perfume in
Has it any disadvantages in
use e.g. does it leave streaks on glasses washed in the detergent
between laboratory trials and launching a detergent powder on a
scale may be anything from six months to three years depending on time
for consumer trials necessary plant alterations stability testing etc.
asked to recommend an additive for any particular proposed formula the
manufacturer must weigh all these points carefully and if necessary
extensive tests. There is no one additive which will perform
with all formulae and the additive makers have constantly to be
new and improved products particularly in view of such developments as
increasing use of primary alkyl sulfates in all purpose formulae.
Alkylolamides in Shampoo Formulations
dialkylolamides are widely used in liquid and liquid cream shampoo
formulations. They exhibit additive powers so far as volume of foam
also help to ensure the creamy thick lather desired by the customer.
of great assistance in thickening liquid shampoos and by their addition
alkylolamine neutralized lauryl sulfate practically any desired
They may be
looked upon as amides derived by condensing an aliphatic acid of
long chain length with an amino alcohol.
it does not necessarily
follow that amides actu ally used are produced by direct condensation.
will be derived from any of the natural fatty acids in the range of
to oleic and stearic and behenic.
class I are waxy materials and on their own are substantially insoluble
water. The members of this class derived from the fatty acids of
length such as lauric and myristic can however be soluble in water when
form part of a composition with other synthetic detergents which are
water soluble. These particular alkylolamides have the power of
soil removal efficiency of other detergents particularly sulfated and
sulfonated detergents such as sodium lauryl sulfate and sodium dodecyl
sulfonate. They also have the power of enhancing the foaming powers of
detergents particularly those just named under the appropriate
falling in class (1) but derived from higher fatty acids are
insoluble in water and do not improve the lathering power or soil
efficiency of detergents but they are valuable emulsifying agents and
cases they serve to render translucent detergent compositions opaque or
appearance. It is also stated in the literature that certain
derived from higher unsaturated fatty acids are useful as conditioning
for the hair when incorporated in shampoos. The alkylolamides derived
lauric and myristic acids which are probably the most used in this
generally chosen to enhance the foaming or detergent power of other
active agents in preparations which are to be marketed as powders.
speaking these alkylolamides even in the presence of substantial
sulfated anionic detergents are not sufficiently soluble to enable
translucent liquid preparations to be formulated. However under some
in the presence of other materials which act as coupling agents clear
products can be produced. The coupling agents may be aliphatic alcohols
even be alkylolamides derived from other fatty acids. As an example of
latter it may be noted that the mono ethanolamide derived from coconut
fatty acids which will contain approximately 65 per cent of the lauric
myristic ethanolamides is much more soluble in liquid detergents
than an alkylolamide derived from pure lauric or myristic acid.
alkylolamides falling in class (2) are more soluble than those in the
class. Until recently the alkylolamides in this class were most
not as the pure amides represented by the formula given but in the form
complex composed of genuine amide free amino alcohol and some soap.
considerable evidence that the complex does not function as simple
in this form many alkylolamides of class (2) are readily soluble in
although they may be salted out by electrolytes under certain
their solubility in water di alkylolamides derived from lauric or
and diethanolamine in the form of the complex containing excess
have found extensive application in the formulations of liquid
preparations. These alkylolamides have the power to augment the foaming
of other surface active agents under certain conditions and at the same
they have a thickening effect upon liquid detergent preparations
Unlike the products in class (1) which are purely effective as
other detergents the alkylolamides in this class possess in the form of
complex very considerable detergent power in their own right and are
used without the admixture of other surface active agents in the
the general cleaning and so called sanitizing detergent preparations.
alkylolamides represented by formula (3) are interesting in that the
may be altered by varying the number of molecules of ethylene oxide in
radicals attached to the nitrogen atom. Compounds in this group show
able wetting properties and the precise wetting power depends upon the
of the molecule. Thus if RCO is derived from short chain fatty acids
lauric or myristic the wetting power is at its highest when the side
not more than five molecules of ethylene oxide (in other words when m+n
formula does not exceed 5). Whether RCO is derived from a longer fatty
such as stearic or oleic it is necessary for the hydrophilic properties
molecule to be increased to achieve optimum wetting power. In this case
best results are obtained when the number of molecules of ethylene
about 10 (that is where m+n = 10). The alkylolamides however in this
never become as extensive in use as the alkylolamides in the other two
They are principally of interest for their value as emulsifiers. The
from coconut oil fatty acids and containing 10/50 molecules of ethylene
are good oil in water emulsifiers for carnauba wax.
Pure Di Alkylolamides
alkylolamides in class (2) have generally been available and used in
of a complex. This was in many ways convenient as the complexes were
soluble and possessed better wetting and detergent power than the pure
also because it is simpler and therefore cheaper to manufacture this
product free from undesirable by products if an excess of alkylolamine
present. Where however these products are used in conjunction with
detergents to enhance the foam of the latter the effective material is
amide while excess diethanolamine contained in the complex does not
towards the effect. In cases such as these the di alkylolamides can
adequately solubilized by the sulfated detergent and therefore the
diethanolamine serves no useful purpose.
of applications however the whole issue would seem to hinge on the
price one is
paying for 100 per cent active amide when one buys it in the nearly
pure state as
compared with the conventional complex. It cannot of course be
that where di alkylolamide is being used as a detergent in its own
or with only minor amounts of other detergents the complex will of
preferred on account of its allround greater solubility and wetting and
has been taken in the production of phosphoric acid esters of the
alkylolamides. These have been claimed to have an anti static effect
in the washing of synthetic fibres such as nylon. Other phosphoric acid
of alkylolamides have found application to produce a pearly effect in
types of cream shampoos.
far described where they have been soluble in water and possessed
active properties have been essentially non ionic in their behaviour.
possible by preparing the acid esters of sulfuric acid or phosphoric
these alkylolamides to produce detergents which are anionic in their
In general the mono alkylolamides falling in class (1) are preferred
sulfation or phosphorylation. The sulfated mono alkylol amides of
fatty acids have excellent lathering power comparable with that
sodium or triethanolamine lauryl sulfate. They show a superior
the latter materials and also greater ability when in dilute solution
dirt particles in suspension.
alkylolamides however are not one of the big volume detergents and they
never equaled the alkyl sulfates in popularity. Probably one of the
this is that it is extremely difficult to control the sulfation
ensure that the finished product is free from undesirable by products
impair efficiency. The fact that on paper the preparation of sulfated
alkylolamide detergents appeared relatively easy at one time tempted
to try and produce these materials without adequate research. The
products however were very variable and frequently contained
amounts of undesirable side products. Properly prepared however the
alkylolamides are excellent products. Probably the best known of this
detergent is the sulfated monoethanol amide or isopropanolamide derived
coconut oil fatty acids. Detergents have been prepared however from
unsaturated fatty acids and though under some conditions they lack the
lathering power of the products from coconut oil they do possess
good detergency and also incidentally exceptional power to disperse
sulfated fatty alcohols are generally processed so as to ensure the
degree of sulfation and the minimum residual amount of unsulfated fatty
alcohols it is not usual in the case of such materials as coconut oil
acids monoethanolamide to secure such a high degree of sulfation.
percent to 85 percent sulfation is the maximum desired. The reason for
that unsulfated and unsulfated material is vary effective in use.
containing as much as 50 percent unsulfated material (provided always
are free from undesirable side reaction products) have excellent
patents which referred to the use of alkylolamides in detergent
were mainly concerned with the improving effect that the alkylolamides
upon the soil removal efficiency of other detergents.However
today are most frequently added to detergent compositions in order to
the lathering power under the conditions of use. When we come to
to estimate quantitatively the effect of the alkylolamides the position
no means simple. Many compositions in practical use are improved by the
presence of an alkylolamide. However it is not always easy to measure
improvement quantitatively under laboratory conditions. For example it
quite useless attempting to infer how a shampoo composition will behave
of the hair by measuring the foam obtained by shaking solutions of the
detergent preparation in measuring cylinders in the laboratory.
way consists in devising a laboratory test which simulates the actual
conditions under which a detergent product is to be used. The effect
alkylolamide exerts upon the foam of a preparation when the foam is
narrow capillary in a relatively narrow foam cylinder is quite
that exerted when the foam is produced on a wide surface area such as
in a sink during dishwashing operation. The conditions which apply
shampooing operation on the hair are different again. It is further
important that in tests designed to evaluate detergent preparations in
laboratory soil such as would be expected in actual practice should be
It is also important that the tests should be carried out at the same
detergent concentration as would apply in practice.
concentrations on lathering power is readily illustrated by an example
concerning the sulfated alkylolamides. Salts of sulfated lauric acid
ethanolamide possess excellent lathering power at high concentrations
might be employed in shampooing or for the washing of clothes under
conditions but if a solution of the detergent is excessively diluted
detergent concentration falls below a certain critical level the
disappears. Sulfated alkylolamides derived from C19 unsaturated acids
quite differently. These give however at a similar concentration level
at which the sulfated lauric mono ethanolamide would have ceased to
produce extremely stable foam. The detergent concentration in a washing
in a commercial laundry would be at a low level.
interesting method for testing a shampoo product under pratical
recently been described in the literature. The effect of alkylolamides
sulfated and sulfonated anionic detergents is not normally to improve
lathering power of the detergent in plain water. Alkylolamides offset
deleterious action of oily or fatty soiling matter on the foam of these
detergents. Many anionic detergents though they lather well in plain
to lose their lather to an astonishing extent in the presence of oil
soiling matter and this effect is prevented by the use of suitable
alkylolamides. The effect however is not quite true at all
the effectiveness of the alkylolamide only takes place above a certain
threshold concentration of active detergent in solution. Fortunately
threshold concentration where lauric or myristic monoalkylolamides or
dialkylolamides used in conjunction with such detergents as the
sulfonates or alkyl sulfates is below the concentration at which most
washing operations are carried out.
of much higher threshold concentration is capable of improving the
anionic detergents at high concentrations (e.g. 3 per cent and over)
would be used when shampooing the hair. Where however the dilution
greater the lathering power rapidly diminishes. Thus using this
alkylolamide it is possible to prepare a composition which yields rich
foam on the hair but immediately the rising operation commences the
disappears. This effect would notappeal to consumers who like to judge
lathering power of a shampoo by the amount of lather to be seen in the
after rinsing. However it would appeal to those who find stable
difficult to rinse away down the sink and to the sewage authorities who
stable detergent foams so difficult to handle.
commonly used alkylolamides for the purpose of stabilizing foam are the
which fall in class (1) and the alkylolamides which fall in class (2)
from either lauric or myristic acids. Products derived from mixed fatty
containing substantial proportions of lauric or myristic acid such as
oil or palm kernal fatty acids are also used. In general however when
to measure effective foam stabilization as such it is generally found
products derived from mixed fatty acids associated with them behave
as no more than inert diluents although in the case of the
from mixed fatty acids sometimes have the advantage of greater
liquid detergent preparations. Therefore it is frequently a better
proposition to buy what is initially a more expensive product devised
fractionated lauric acid than to use a mixed product which has a lower
observations apply to the stabilization of foam and there are of course
aspects of the use of alkylolamides where the mixed products may be
worthwhile. Generally the lauric monoalkylolamides are preferred for
powder compositions. Frequently they are here associated with
in the case of some alkylolamides particularly isopropanolamides the
polyphosphates seems to be necessary for the maximum stabilising effect
produced. The monoalkylolamides are generally dispersed in detergent
an elevated temperature before it is mixed with the phosphates or other
builders and fed to the spray drier. Mono alkylolamides are now
powder form which greatly facilitates the operation of dispersing them
detergent slurry. Lauric diethanolamides either in the form of complex
previously referred to or in the pure state are used in the formulation
liquid detergents since they do not impair the cloud point of these
In actual fact diethanolamides in the form of the complex frequently
effectively lower the point at which alkylaryl sulfonate and other
cloud. However there is no hard and fast rule concerning the use of the
different types of alkylolamides. Dialkylolamides may be incor porated
powders in quite significant amounts and on the other hand mono
may be included in liquid composition either in restricted amounts
solubilized by the addition of alcohol.
covers polymers derived from monomers that have a vinyl group attached
aromatic ring (1). It does not cover aromatic monomers having a
the ring styrenes or except for 4 vinylbiphenyl Substituted styrenes.
monomers are general1y prepared by dehydration of the corresponding
can usually be obtained by the acetylation of the corresponding
reduction of the ketone. The carbinol can also be obtained by the
the aryl Grignard reagent with acetaldehyde (eq.1)
Table 1 are listed some
vinylarene monomers and their physical properties.
anionic homopolymerization of 1 vinylnaphthalene 2 vinylnaphthalene and
vinylanthracene in tetrahydrofuran at 25°C have been determined and
rate constants of 500 300 and 0.2 l mole 1 sec 1 found. The greater
of 1 and 2 vinylnaphthalene as compared with that of styrene has been
attributed to their lower localization energies.
polymerization of 9 vinylanthracene produces only low molecular weight
initation by naphthalene or biphenyl radical anions or by butyllithium
oligomers having a DP of 4 12. A study of the reaction has shown that
the concentration of the living ends remains unchanged during the
degree of polymerization does not correspond to the concentration of
indicating an efficient chain transfer reaction. When additional
supplied to the polymerized system more polymer forms without affecting
molecular weight thus indicating that no chain transfer to polymer
It has been
shown that 9 vinylanthracene can polymerize both along the vinyl group
across the central ring of the anthracene system and structural
shown that material polymerized in the presence of lithium potassium
contains a lower percentage of anthracene rings than material
polymerization mechanism shown in equations 2 4 has been proposed.
physical and chemical evidence indicates that the predominant structure
polymer is that resulting from a 1 6 across the ring addition. To
the low molecular weight of the polymer the chain transfer reaction
equation 5 has been proposed.
of the anionic polymerization of acenaphthylene has shown that the
follows pseudo first order kinetics and that a chain transfer reaction
monomer similar to that observed for 9 vinylanthracene takes place. The
molecular weight that could be obtained by anionic polymerization was
thermal polymerization in bulk produced polymers having very high
weight (ca 2 000 000). Although the chain transfer mechanism has not
established it probably involves electron transfer to monomer coupled
hydrogen abstraction from solvent. The copolymerization of 1
with 2 vinylpyridine and with styrene has been investigated in both
and simultaneous polymerizations and good yields of copolymers were
when 1 vinylnaphthalene was initiated with a polystyrene anion.
results are reported when styrene is initiated with a poly(l
anion addition of two or three equivalents of styrene to living poly(l
vinylnaphthalene) leads to the disappearance of the characteristic 558
maximum of the poly(1 vinylnaphthalene) anion but the expected 340 mm
of the polystyrene anion does not appear. Instead a new absorption peak
mm appears but on standing for 24 hr the original 558 mm peak of poly(l
vinylnaphthalene) reappears. When a large excess of styrene twentyfold
or more is
added the characteristic spectrum of polystyrene appears permanently.
were explained by assuming that the reaction involves three steps (eqs.
the first styrene molecule produces a benzyl type anion that froms a
the preceding naphthalene group. The product resembles the adduct of living Polystyrene and
thracene and the
product very slowly adds a second molecule of styrene. The addition of
second molecule destroys the complexing with naphthalene and the
polymer propagates as ordinary polystyrene does.
formed on addition of a small excess of styrene to living poly(l
vinylnaphthalene) must be unstable because the spectrum of the poly(l
vinylnaphthalene) reappears within 24 hr. It has been concluded that
formation of the complex is reversible and that the equilibrium
of styrene is given by the reaction shown in equation 9. The reaction
must however contain some living polystyrene anions since some segments
added two or more styrene units. Hence another equilibrium is
10). These three equilibria are coupled in the overall process and the
equilibrium of the overall process favors the right side (eq. 11). This
has been tested with a methylstyrene the propagation of which is
thermodynamically unfavorable and a stable complex was formed when this
was added to living poly(l vinylnaphthalene).
copolymers of 4 vinylbiphenyl and isoprene have been prepared using
techniques Because of difficulties in achieving a rigorous purification
vinylbiphenyl a coupling technique was used whereby the A monomer was
polymerized first the B monomer was then added and the AB anion was
coupled with a reactive dihalide. Using this technique the residual
in the A monomer only destroy some initiator by estimating the degree
it is easy to use a slight excess of initiator to compensate for the
destroyed by the impurities Coupling of the AB anions was achieved by
phosgene which was allowed to diffuse very slowly into a vigorously
copolymers were characterized by gel permeation chromatography and from
knowledge of the ratio of the refractive index increments of the two
homopolymers and the overall composition a quantitative analysis was
an electron from alkali metals to an aromatic hydrocarbon such as
or biphenyl is well known. The same reaction occurs when the vinylarene
is attached to a polymer chain. The products have been referred to as
polyradical anions and are formed experimentally in all glass
systems by the reaction of the polymer in tetrahydrofuran with a sodium
at temperatures ranging from 80 to 30°C.
products have been characterized by viscometric spectrophotometric and
spin resonance measurements. It was found that the viscosity of the
decreases with time and that the final viscosity depends essentially on
alkali metal concentration. Spectrophotometric data have shown that
the spectrum becomes almost identical to living polymer dianions and
spin resonance studies have indicated the presence of unpaired
concentrations proportional to the sodium content. The disappearance of
signal to practically zero the formation of anions and the decrease in
viscosity with time are consistent with a cleavage mechanism in which
electron migrates from the aromatic ring to the a carbon of the
with formation of a negatively charged end (eq. 12). The same mechanism
been proposed for poly (N vinylcarbazole) poly (l vinylnaphthalene)
vinylnaphthalene) and poly (4 vinylbiphenyl). Poly (acenaphthylene)
fast that it is not possible to follow changes in viscosity as a
time. It has also been found that monomeric fragments are produced (eq.
anions have been used to initiate graft polymerization reactions. The
is not applicable to monomers that polymerize by an electrontransfer
only homopolymerization is achieved. However monomers such as cyclic
that cannot polymerize by an electron transfer process but do
do form graft copolymers. The mechanism of the polymerization is
that proposed for the carbonation of the naphthalene radical anion
vinylfluorene) has been metalated with metallic sodium or lithium or
corresponding naphthalene radical anions (eq. 17) and graft copolymers
variety of vinyl monomers such as styrene methyl methacrylate or
in addition to ethylene oxide have been prepared.
vinylnaphthalene units incorporated into a copolymer has also been used
provide sites for anionic grafting reactions. Thus a copolymer of
containing small proportions of 2 vinylnaphthalene has been prepared by
radical copolymerization techniques the resulting copolymer metalated
butyllithium and styrene or 2 vinylnaphthalene graft copolymerized on
anionic sites. The resulting materials exhibited elastomeric properties
to those of styrene butadiene ABA block copolymers provided the number
grafts per backbone was small.
stereoregular polymerization of styrene and substituted styrenes has
considerable attention other vinylarene monomers have been studied much
extensively. Natta and co workers have surveyed the stereoregular
polymerization of over 20 vinyl aromatic monomers among these were1
vinylnaphthalene 2 vinylnaphthalene 1 vinyl 4 chloronaphth alene 1 2 3
tetrahydro 6 viny1 naphthalene 4 vinylbiphenyl 9
9 vinylanthracene. This study established
that Ziegler Natta polymerizations are very sensitive to steric
the double bond and when the steric hindrance is excessive such as in 9
vinylanthracene no polymerization takes place. Although one study does
polymerization of 9 vinylanthracene in yields from 20 to 90% depending
Al/Ti ratio with an Al (C2H5)3 TiCl4 catalyst system the
results indicate a cationic
polymers of 1 vinylnaphthalene 2 vinylna phthalene and 4 vinylbiphenyl
been prepared using a (C2H5)3Al TiCl4 (C2H5)2AlCl TiCl3 or (C2H5)3 AI
catalyst system . The latter catalyst gave polymers in 75 95%
were at least 90% isotactic. The atactic fraction could be separated
isotactic ones by extraction with methyl ethyl ketone. The isotactic
were also characterized by infrared and nuclear magnetic resonance
stereoregular polymers could be crystallized. In polymers in which
factors lead to a crystalline phaseNot all stereoregular polymers could
crystallized. In polymers in which steric factors lead to a crystalline
that would have a lower density than the amorphous phase no
took place. Thus only 1 vinylnaphthalene produced a crystallizable
x ray diffraction study on this polymer has been carried out. The Bragg
distances in the unit cell are a = b = 21.20 Å and c = 8.12 Å and the
gravity is 1.12.
stereoregular ionic polymerization of acenaphthylene has been
some detail. Although four stereoisomers can be written eg cis and
isotactic and cis and trans syndiotactic a study of molecular models
that only the trans isotactic and trans syndiotactic conformations can
polymers. The trans isotactic poly(acenaphthylene) forms a helix and
the trans syndiotactic
poly (acenaphthylene) forms a stair stepped rigid rod. These
obtained by n butyllithium or boron trifluoride polymerizations and
characterized by infrared and nuclear magnetic resonance spectroscopy.
has also been polymerized with an Al(C2H5)3 Ti(OC3H7)4 catalyst system
mention of stereoregularity was made.
polymerization of vinylarene monomers other than styrene is not well
and little reliable quantitative information is available.
readily forms polymers of high molecular weight although a dimer can be
obtained when a solution of acenaphthylene in glacial acetic acid is
with a small quantity of concentrated hydrochloric acid. The kinetics
cationic polymerization catalyzed by boron trifluoride and iodine has
studied. In the first case a second order reaction with respect to
trifluoride was observed and in the second case a high order reaction
respect to iodine concentration and cocatalysis by hydrogen iodide was
radical polymerization the cationic polymerization of 9 polymerization
Early studies assumed a normal vinyl polymerization but it was later
the normal addition takes place to only a very minor extent and that
polymerization across the ring similar to that already discussed in the
polymerization takes place. A wide variety of catalyst systems and
also investigated.Very little information is available on the cationic
polymerization of other vinylarene monomers. l Vinylnaphthalene
be polymerized to a high molecular weight product but monomers
the a or b position of the vinyl group yield mainly dimers. The
of 4 vinylbiphenyl with Friedel Crafts catalysts has been reported and
vinylpyrene and 2 vinylfluorene have also been polymerized with BF3.
ions such as tropylium hexachloro antimonate
tetrafluoroborate (C7H7 BF4
have been used to initiate the polymerization of acenaphthylene and 1
Free Radical Polymerization
the 2 2 azobisisobutyronitrile initiated bulk polymerization of 1
vinylnaphthalene have been reported. The polymerization rate is
the 1/2 power of the initiator concentration and the first power of the
concentration. The molecular weight of the polymer was shown to be
by a chain transfer reaction with the monomer and a chain transfer
0.03 about 300 times that for styrene was found. As a consequence only
molecular weight polymers (2000 6000) were obtained. The bulk
2 vinylnaphthalene leads to a product having a molecular weight of
000. Emulsion polymerization techniques yielded a poly(l
having a molecular weight of 25 000 and a poly (2 vinylnaphthalene)
molecular weight of 115 000.
ease of bulk polymerization of 1 vinylnaphthalene 2 vinylnaphthalene 6
vinyl 1 2 3 4 tetrahydronaphthalene and
vinyldecahydronaphthalene has been compared 1 and 2 vinylnaphthal enes
easiest to polymerize 6vinyl 1 2 3 4 tetrahydronaphthalene had
rates comparable with those of unsubstituted styrene and
vinyldecahydronaphthalene did not polymerize during 30 days at 100°C.
postpolymerization of 60Co g irradiated 2 vinylnaphthalene has been
The monomer was irradiated at 78°C and then postpolymerized at
ranging from 20 to 41°C. A limiting conversion of about 40% was
soild state polymerization under pressure has also been investigated.
polymerization rates of 1 and 9 vinylanthracene and 9 vinylphenanthrene
also been compared. The highest reactivity was shown by 9
the lowest by 9 vinylanthracenc. The reactivities were explained on the
of steric hindrance to conjugation between the ring system and the
and the nonaromatic character of the 9 10 double bond in phenanthrene.
radical polymerization of 9 vinylanthracene proceeds so slowly that it
little promise as an acceptable polymerization technique. No studies
reported in which the structure of this polymer has been examined.
can be polymerized to a high molecular weight polymer using free
initiators and a molecular weight of over 150 000 has been reported.
kinetics of the thermal polymerization of a highly purified sample have
studied dilatometrically and a high activation energy for both
propagation was found.
high pressure on the free radical polymerization of acenaphthylene has
been investigated. It was found that the rate of polymerization is not
increased as much by pressure as is that of other olefinic monomers
styrene. The effect of pressure on molecular weight was also less than
polystyrene and the molecular weight of the polymer increased by a
2.6 between 1 and 2880 atm.
polymerization of acenaphthylene initiated by x rays has been studied
in air in
nitrogen and under vacuum. The results indicate that the molecular
essentially independent of the total dose rate and the rate of
is proportional to the first power of the dose rate. The polymer was
as indicated by x ray diffraction.
polymerization rates of a series of substituted vinylbiphenyls have
to be first order in monomer and they were claimed to increase with
conjugation and polarity of the substituents. Reactivity ratios for
vinylarene monomers are shown in Table 2.
As indicated by the 1/r1
values all vinylarene
monomers shown with the exception of 9 vinylanthracene are more
copolymerization than is monomer M1.
A series of
copolymers of 4 vinylbiphenyl with styrene and vinylchlorobiphenyl and
vinylfluorobiphenyl each with a methylstyrene or a p dimethylstyrene
prepared by mass and emulsion copolymerization. The 4 vinylbiphenyl
copolymer was claimed to have improved resistance to heat distortion.
styrene on bulk polymerization rates and molecular weights of
various vinyl naphthalenes has received considerable attention. Thus
polymerization rateof 1 vinylnaphthalene is decreased by the addition
styrene and the rate reaches a minimum with 60 mole % styrene in the
general the addition of styrene to vinylnaphthalene increases the
weight of the copolymer. With 1 vinylnaphthalene addition of styrene
effect until about 60% had been added and then the molecular weight
almost linearly from 20 000 to 110 000. The increase in molecular
weight of poly(2vinylnaphthalene)
by addition of styrene was in general more gradual but was more rapid
styrene concentration. The same effect was also noted in methyl
vinylnaphthalene copolymerization. As in homopoly merization emulsion
produce copolymers having higher molecular weights relative to those
by bulk polymerization.
styrene to 6 chloro 2 vinylnaphthalene leads to increasing rates with
increasing styrene content in the feed whereas the opposite is true
chloro 1 vinylnaphthalene. The addition of methyl methacrylate has
little or no
effect on 4 chloro l vinylnaphthalene but decreases the rate of
copolymerization of 6 chloro 2vinylnaphthalene.
copolymerization behavior of anthracene and phenanthrene derivatives
styrene has been investigated. The same order of decreasing activity (9
vinylphenanthrene> l vinylanthracene > 9 vinylanthracene)
as in homopoly
merization is also noted in copolymerization. Although the rate of
of 9 vinylanthracene with styrene is faster than that of 9
alone 9 vinylanthracene feeds greater than 25% by weight inhibit the
polymerization of styrene 2 And 3 vinylphenanthrenes have been
with methyl acrylate. Even though both monomers are more reactive than
toward methyl acrylate radicals the addition of methyl acrylate to
the phenanthrenes reduced both the molecular weight of the polymer and
copolymers of 1 vinylpyrene have been prepared and their softening
copolymerization of acenaphthylene with other vinyl monomers has been
described. Of these the most extensively investigated was the
of styrene with acenaphthylene. Mass polymerizations using peroxide
or thermal polymerizations at 120 125°C for as long as 10 days yielded
molecular weight copolymers. However emulsion polymerization at 30°C
catalyst systems gave excellent yields and high molecular weight
of acenaphthylene styrene and butadiene have also been prepared.
has been copolymerized with divinylbenzene and the crosslinked network
sulfonated. Strongly acidic ion exchange series were thus produced.
induced copolymerization studies of acenaphthylene with acrylamide and
anhydride have been carried out. Only polyacrylamide homopolymers could
obtained in attempted copolymerizations of eutectic mixtures with
acenaphthylene. Solid state copolymerizations of maleic anhydride with
acenaphthylene produced 1 1 copolymers.The same alternating copolymer
obtained in free radical solution copolymerization.
of acenaphthylene onto polyethylene have been prepared by roll mixing
polyethylene acenaphthylene and benzoyl peroxide in air at 100°C.
grafting was obtained at 30 min and thereafter the amount grafted
because the grafted branches were selectively masticated. No grafting
obtained in the absence of benzoyl peroxide.
In Table 3 are collected the parameters for the Mark Houwink equation
vinylarene polymers correlating intrinsic viscosity with molecular
studies have shown that the coil size of poly (2 vinylnaphthalene)
of polystyrene by a factor of 1.4 indicating that substitution of
benzene by a
naphthalene ring increases the thermodynamic stiffness of the polymer.
study has shown that even though considerable hindrance to rotational
chain segments should be expected in poly (acenaphthylene) its dilute
behavior indicates that it has a hydrodynamic volume comparable with
polystyrene. It has also been shown that poly (4 vinylbiphenyl) poly (l
vinylnaphthalene) and poly(2 vinylnaphthalene) can be represented by a
plot of intrinsic viscosity times the molecular weight of the repeat
versus weight average degree of polymerization and that they also
common gel permeation chromatography calibration plot. These results
the some what surprising conclusion that all these vinylarene polymers
similar hydrodynamic volumes. Poly (acenaphthylene) could not be
these studies be cause it has been found to be unstable in solution and
degrade by a free radical mechanism that is at least partially an
A number of
charge transfer complexes have been prepared in which the electron
donor is a
vinylarene polymer. They are of interest because the complexes are
show semi conductive properties in the solid state.
N Acyl N Alkyltaurates
N acyl N
alkyltaurates have a general formula RR`NCH2 CH2SO3Na where R may be
taIl oil or taIlow group and R may be a methyl or cyclohexyl group.
most commonly used and produced product in this group of compounds is
Oleoyl N methyltaurate. It is sold throughout the world under various
names most common among them being IGEPON T.
first introduced by I.G. Farben industries in Germany and is still in
market in its original form. It is sufficiently stable for most textile
processing work except the carbonizing of wool where a strong sulfuric
bath is encountered. Igepon T has enjoyed a steady expansion of market
present time in U.S.A. and Germany and most other developed countries
of the advent of alkyl benzene sulfonates. In India however most of its
requirements are met through imports.
In a more
general formula of N acyl N alkyltaurates
represents hydrocarbon radicals of the fatty acid series which for
reasons may contain twelve to eighteen carbon atoms. R2 represents an
cycloaliphatic group which should range from one to eight carbon atoms.
carbons in Rl and R2 preferably should not be less than twelve nor more
twenty one. Beyond these limits the quality of the product falls off
one of several properties. R3 may be a metal or an organic base or
computation of the number of possible products under the above stated
might reach 1000.
changes in structure is fairly well defined. Little detergency is
unless Rl and R2 combined contain at least twelve carbon atoms.
increased by increasing the length of either Rl or R2 or both. The
reached at approximately sixteen carbon atoms for Rl if the chain is
and saturated. If unsaturated then maximum detergency occurs at
carbons and it is believed that with more unsaturation the maximum
carbons is further increased Departures from straight chain in R1 by
or by introduction of a solubilizing group will de crease detergency
increase the wetting power. A decrease in the length of Rl increases
solubility and wetting power. If Rl is kept within twelve to sixteen
atoms and if the size of the R2 group is increased from a methyl to a
homolog such as the butyl or amyl group the resulting Igepon becomes
soluble inspite of the molecular weight increase. If Rl is twelve
solubility of the Igepon passes through a maximum when R2 is a four
straight chain. Wetting increases with increase in the lengths of R2
and R2 combined contain approximately eighteen carbons. Further
increase in R2
brings on a decrease in wetting. R2 may be hydrogen but when a taurine
a substitution of at least one carbon group enhances the properties of
resulting product tremendously. The choice of a metal for R3 may affect
and the power to emulsify and disperse other substances. There is
difference in solubility between the sodium and potassium salts in the
compounds investigated. The calcium salts are much less soluble. The
representative types of Igepon T currently manufactured in developed
such as U.S.A. and Germany are given in Table 1.
primary factor in determining which Igepon type compounds will be
important is the cost of raw materials the economic limitations stilI
relatively wide area of investigation. The product derived from oleic
acid and N
methyl taurine provides the optimum combination of desirable proper
compound is further recommended by the relatively low price of its raw
Applications of Igepon T Products
its greatest use today in the textile field where it was first
finds its way into almost every phase of textile wet processing. The
list of uses
include scouring wetting out degumming kier boiling dye leveling dye
and peroxide bleaching fulling lime soap dispersing and finishing. It
finds application in agriculture paper leather and metal cleaning and
also to a
small extent in household products including dentrifices shampoos
pharmaceutical preparations. It is also used in the scouring of
electrolytic plating baths in the washing of automobiles airplanes rail
coaches and locomotives rugs floors buildings and for cleaning streets
roads and in the dairy food and for industries.
prepared in a variety of forms. One is a clear liquid suitable for
incorporation into consumer products. It looks much like a conventional
soap and is available with 15 and 25 per cent active ingredients.
is a slurry or an opaque heavy liquid. This material contains 28 per
active ingredients and is essentially the product as it comes from the
condensation kettles it contains no added chemicals. It may be used by
formulators who will process it further by adding it to other
drying it to a powder. It can be shipped in tank cars and is the least
expensive of the various Igepons.
Future of Igepons
Igepon T its analogs and homologs is bright. The economic existence of
type of product is assured by the fact that the biggest weight in its
is a fatty acid. The principal fatty acid used is oleic acid which is
abundantly in vegetable and animal oils. As synthetic detergents
non fatty soures encroach on the soap market the fats and particularly
from which oleic acid is largely derived will tend to become more a
advantage enjoyed by the taurine type Igepon (N acyl N alkyltaurates)
fact that the Igepon T gel largest seller in the group today is not the
wetter in the series nor is it the best emulsifier or dispersant. It is
best foamer the best textile softening agent or lime soap dispersant
nor is it
the most soluble member of the group. It has a good high average on all
which led its developers to call it the universal soap. The taurine
can be modified to well over 100 varieties. Any one of the various
properties may be obtained to a high degree by making changes in the
of the 1gepon molecule. Consequently it is predicted that the 1gepon
surfactants will have an important future in the development of special
products where price is not the primary consideration.
Manufacture of Igepon T
major materials required for
the production of sodium N oleoyl N methy ltaurine are oleic acid
N methyltaurine and caustic soda. It is extremely important that a high
of oleic acid be used in the process. If an excessive amount of esters
unsaponifiable material is present the resultant Igepon will have an
free fat which tends to make the gels cloudy.
methyItaurine may be used as a 25 to 30 percent filtered aqueous
30 and 50 per cent caustic soda solutions and the hydrochloric acid
control the pH of the batch at various points in the processes can be
standard commercial products.
Oleic Acid Chloride
in manufacturing Igepon T gel or Igepon T powder is the production of
acid chloride (oleoylchloride) from oleic acid and phosphorous
Acid chlorides other than oleic may be used to make special Igepon
takes place in a jacketted lead lined kettle equipped with both cooling
and low pressure steam connections. A horse shoe type agitator stirrs
charge. A 1.5 lead vent to the roof of the building removes volatile
and decomposition products of phosphorous trichloride from the kettle.
essential that the kettle be dry before charging is begun to prevent
of the phosphorous trichloride. If any condensation accumulates on the
due to extended inactivity it is driven off by introducing steam into
jacket while the kettle is empty.
operation oleic acid is blown by air from a feed tank to a steel weigh
trichloride is similarly blown into a lead lined weigh tank. A 400 kg.
of acid is drawn from the weigh tank and dropped by gravity into the
Phosphorous trichloride (103 kg.) at room temperature is introduced
weigh tank over a period of one hour while cooling water is circulated
the jacket of the kettle. A sight glass in the lead line through which
phosphorous trichloride is charged permits the operator to judge the
of this stream. After the kettle has been completely charged the
raised. to 50°C to 52oC and is held there for 6 hours by introducing 15
steam into the jacket. At the end of this period the temperature is
60°C for an additional 15 minutes to ensure completion of reaction.
cent of excess phosphorous trichloride is used in the process. This
38 kg. is partially retained in solution in the fatty acid chloride and
in the final product as phosphite salt.
product is blown by air pressure into two lead lined cone shaped tanks
allowed to stand over night settle out the by product phosphorous acid.
bases of the cones are heated with extended 1.5`` lead steam coils to
the heavy acid sludge and aid in the separation. After drawing off the
waste acid the contents of the cone tanks are agitated and then a
separation of acid is drawn off. The point of separation is determined
observation through sight classes in the draw off lines. The spent acid
piped direct to the sewer through lead pipes traced with 1.5 outside
pipes carrying low pressure steam.
achloride will descompose on standing if exposed to atmospheric
consequently it is made up only as needed and is piped through steam
lead lines direct from the cone tanks to the weigh tanks of the Igepon
made in a brick lined kettle equipped with a four fingered stainless
agitator. A stainless steel submerged coil provides temperature
kettle has stainless steel feed lines for oleic acid chloride and
acid and caustic solution a stainless steel thermometer well and a lead
pipe. Air for forcing the charge out of the kettle is introduced into
steel kettle equipped with an anchor type agitator is also available.
temperatures in this kettle are controlled by a steel jacket connected
steam and cooling water lines. Inlets and vents are arranged similarly
in the larger kettle.
batch 25 to 30 percent aqueous solution of N methyl taurine is blown
the storage tanks until an amount of solution equal to 89.25 kg. of N
methyltaurine has entered the weigh tank. The correct gross weight of
charge based on the N methyltaurine analysis of the storage tank is
the operator by the analytical laboratory. This charge is then dropped
gravity into the reaction kettle and the flow of cooling water is
the jacket to bring the temperature of the charge down to 22° to 25°C.
weighed in the same weigh tank is then added to bring the total weight
charge at that point to 1296 kg. Addition of 30 per cent aqueous
solution is begun and when the equivalent of 14.25kg. of sodium
been weighed in oleic acid chloride is introduced from a lead lined
acid chloride enters the kettle through separate perforated stainless
pipes below the level of the initial taurine charge. This practice
the liberation of noxious fumes reduces the corrosive effect of the
chloride above the liquid level and safeguards against side reaction
sodium hydroxide and oleic acid chloride.
addition of the two reactants is continued for 4 to 6 hours until a
43.5 kg. of sodium hydroxide and 214.2 kg. of about 92 per cent oleic
chloride have been charged. The rate of addition of these two solutions
adjusted to maintain a slight stoichiometeric excess of sodium
hydroxide in the
kettle at all time as determined by spot tests on triazine paper 2 (4
tolyldiazoamino 4 sulfobenzoic acid).
reagents have been added the charge is agitated for an additional hour
ensure completion of reaction. Cooling water is circulated through the
maximum flow rate during the entire reaction period. During the winter
the temperature of the charge is about 22°C at the beginning of the
and rises to 27°C. However in the summer time the final temprature may
high as 40°C.
reaction has been completed a sample is taken and the percentage of
methyItaurine is determined by coupling with diazotized mnitraniline.
desirable to have a slight excess of N methyltaurine in theproduct to
that the reaction has gone to completion. After completion of the
hydrochloric acid is added to the kettle through a glass and rubber
a carbon mounted on a platform scale. Acid is added until the charge
slightly red spot test with brilIiant yellow paper (pH 6 to 8). This
neutralization usually requires about 15.3 kg. of acid. In making some
special Igepon products additional hydrochloric acid may be needed at
standard T gel the neutralized batch is diluted to 1734 kg. with water
0.725 kg. of a light floral liquid perfume. The charge is then heated
and held there for 1.5 hours. The charge is blown into white oak gum or
wood barrels. Air used to blow out the batch passes through a trap to
rust particles which would tend to darken the finished product. As a
precaution against contamination a 0.007 opening stainless steel filter
product discharge line removes all solid particles from the liquid
before it enters the shipping containers. The barrels are allowed to
the shipping platform and when the Igepon reaches a temperature of
it sets up as a firm opalescent gel.
T gel may be shipped in polyethylene lined fibre board drums or wooden
The batch yields about 1090 kgs. gel having a composition of 15.3 to
cent Sodium N oleoyl N methyltaurine 0.8 to 1.0 per cent sodium oleate
cent N methyltaurine 4.0 per cent sodium chloride and 78 per cent
represents approximately the theoretical yield.
Igepon T Powder
this product the initial charge of 30 per cent N methyltaurine solution
contains 95 kg. of 100 per cent N methyltaurine and when diluted with
1224 kg. it gives a slightly more concentrated solution than that used
gel process. As a 30 per cent solution 17.6 kg. of sodium hydroxide are
to this intial charge to keep the reaction mixture on the alkaline
226.5 kg. of technical oleic acid ehloride are added simultaneously
kgs. of sodium hydroxide as a 30 per cent solution over a period of 4
to 6 hours
as in gel production.
stirred for 1 hour after charging is completed and any excess of N
methyltaurine is reactcd with additional acid chloride and caustic soda
the production of gel. The completely reacted charge is then heated to
the steam coils and neutralized to the brilliant yellow and point with
hydrochloride acid. Immediately after neutralization 530 kgs. of common
are dumped into the batch from bags and water is added to bring the
weight of the batch to about 2652 kgs. At this concentration about 36
solids the saIt is completely dissolved. It is important that no
solid material remains in the charge because it would plug up the
the spray drier. If the pH of the batch after the addition of the salt
fall between 7.1 and 7.3 sodium hydroxide or hydrochloric acid is added
adjust the pH within these limits.
mixture is blown from the reaction kettles into a 3/8 lead lined sted
tank. The charge is heated to 50°C by lead steam coils in the feed tank
then is pumped to the three 10 gauon feed pots of the spray dryer. The
atomizers use air at 80 Ibs/in2 pressure heated to maintain 501bs.
the injection nozzles to ensure adequate atomization in the tower. Air
to top of the dryer is preheated to about 225°C by an oil fired furnace
forced into the dryer by a centrifugal fan at a rate of about 250 cubic
per minute. The major part of the dried powder is discharged from the
the dryer tower and carried along by the added cold air into the
cyclone separator from which it drops directly into a transfer drum.
per cent of the product however is carried through the cyclone and is
reintroduced into the dryer chamber. A second take off from the dryer
is located just above the bottom taper. This duct carries a more dilute
of air borne powder into a larger secondary cyclone separator. The
fall out in this separator are refluidized by more cold air and
returned to the
top of the primary cyclone. The overhead from the secondary cyclone
7 to 10 percent of the product is introduced into a water scrubber. One
spray above the inlet and three below remove all but about 2 per cent
product from the dryer exhaust. The scrubbed air is vented to the
The liquor is drawn from the bottom of the tower into a storage tank.
water is added to this tank by an automatic level control. A high
pump drawing from the tank recycles water to the spray nozzles and
process water to the condensation kettle.
If a kettle
batch is made each day the dryer feed pots can be kept full and provide
uninterrupted feed to the dryer. Under these circumstances the dryer
as much as 180 to 200 kg. Igepon per hour as it has a rated capacity of
water per hour. The product comes from the dryer as low density
are lightly milled in a paddle mixer to break up the larger lumps and
to mix in
500 grams of a light floral perfume per ton of Igepon. From the mill
is dropped directly into the open top steel drums in which it will be
Yields of powdered product run about 836.4 kg. per batch and analyze
to 32.5 per cent oleoylmethyltaurine 1.5 to 3.0 per cent sodium oleate
to 0.8 per cent N methyItaurine the remainder of the powder comprises
salts. Chief among these is sodium chloride and a trace of sodium
However phosphite salts (about 3 per cent) are also present these are
from the excess phosphorous trichloride dissolved in the oleic acid
The yield is about 91 per cent of theory.
on the Igepon T operation is relatively simple. By experience rule of
knowledge can be accumulated which tells the operators whether the
going properly. At some points analytical samples are taken merely as a
precaution and only analyzed if trouble develops later in the operation.
trichloride oleic acid and N methyItaurine are checked for rigid
each time a shippment of materials arrive at the factory. The acid
charged to the reaction kettle is analyzed the oleic acid chloride
trichloride and free fatty acid. After the condensation is complete the
is checked for pH and residual N methyltaurine. The pH is checked by a
calomel cell pH meter and is then adjusted as explained in the
been adjusted it is checked again and the final shipping sample is sent
laboratory. This final sample is examined for clarity viscosity and
A 10 percent water solution of this sample must be perfectly clean and
have a pH between 7.2 and 7.5 at this point.
powder undergoes an almost identical analysis routine. If the content
oleoylmethyltaurine falls outside of the permissible limits it is
the subsequent batches at the ribbon blender.
the Igepon process steam is used only for process heating. Since the
temperatures required are all reasonably low steam at 100 psi is
this operation. Compressed air is used in the plant for forcing liquids
one vessel to another the 45 psi air is sufficient. The air used for
transfering phosphorous tricoloride is passed through a dryer and
present hydrolysis and contamination. The purifying unit consists of a
trap a steel chamber 12 in diameter and 6 long filled with quick lime
the steam and a similar tank 4 long containing a cloth bag filler to
particles of lime or other solids that might be carried over into the
phosphorous trichloride tanks.
may have a separate compressor which provides 90 Ib/in2 air for
corrosion problem is not critical in the operations as described but
special materials must be used. Carbon steel is suitable for most
However those which must contain phosphorous trichloride or oleic acid
are homogeneously lead bonded. This type of lining is applied by
entire inner surface of the steel vessel and then soldering the lead
plates to the whole steel surface. This technique eliminates the
buckling and blistering. It also means that in the event of failure of
lining only the steel directly behind the gap in the lining is
attacked. In the
so called loose lining technique in which the lead sheets are tacked to
shell only along with seams a failure at any point usually means that
corrosive contents of the vessel will shortly enter the entire space
the lining and the vessel wall. The spray drier feed tank may be lined
fashion but only moderate temperature are encountered in this tank and
agitation is never violent.
general the lead linings in the Igepon process equipment last 7 to 9
before they must be replaced. The reaction kettles may be of stainles
however it is brick lined construction it may require re lining after
each two years. All equipment which comes in contact with finished
Igepon is made of stainless steel. since the detergent will exchange
with ordinary steel to form iron salt which has an undesirable dark
steam lines in the
brick lined kettle are stainless steel in the spray dryer feed tank
lead. The other kettles are equipped with external jackets. Agitators
either lead cov N Acyl N Alkyltaurates ered stainless steel or in the
the spray drier feed tank wooden.Neither stainless steel nor lead will
in the duct which carries the moist exhaust from the spray drier.
high nickel alloy serves well. The spray drier itself is made of carbon
which must with stand static pressure such as those employing air
transfer are entered and inspected and subjected to hydraulic testing
years. Unpressurized steel tanks which store corrosive liquids are on a
inspection schedule. Storage tanks in non corrosive service are
5 years. Kettles are also inspected at 5 years intervals. Jacketed
lifted out of their jackets and the surfaces are cleaned and inspected
pits. Pits usually occur in the welded seams. If the welds are badly
below the surface of the adjacent plates the bead is chipped off and
most of the materials involved in the process are transferred through
by air pressure pumps present only a limited corrosion problem. Where
used they are of motor driven centrifugal type. Where pure oleic acid
pumped a high alloy steel pump is used. All other pumps are of carbon
steel valves are used on all lines which transfer finished liquid
Pipe lines which carry liquid Igepon T also are of stainless steel.
transfer oleic acid chloride are lead lined and steam traced. The steam
is only used in the winter when the acid chloride has a tendency to